WO2021172408A1

WO2021172408A1 - Semiconductor device and production method therefor

Info

Publication number: WO2021172408A1
Application number: PCT/JP2021/007036
Authority: WO
Inventors: 達生長谷川; 暁北原; 井上　悟; 俊人荒井; 光弘井川
Original assignee: 国立大学法人東京大学
Priority date: 2020-02-26
Filing date: 2021-02-25
Publication date: 2021-09-02
Also published as: JPWO2021172408A1

Abstract

[Problem] To provide a semiconductor device including a thin-film transistor that can be more easily produced in comparison to conventional methods. [Solution] Prior to forming an organic semiconductor film upon an insulation film that is lyophobic with respect to a solvent, which is a main component of a solution including a material constituting an organic semiconductor film as a solute, a conductive film that is lyophilic with respect to the solvent is formed in a desired shape. It is thus possible to form the organic semiconductor film at a desired position, such as a channel formation region of the thin-film transistor. In a semiconductor device according to one mode of the present invention, for example, conductive films that are in a lower layer of an organic semiconductor film and above an insulation film functioning as a gate insulation film, and that respectively function as a source and a drain have desired shapes.

Description

Semiconductor devices and their manufacturing methods

One aspect of the present invention relates to a semiconductor device including a thin film transistor. Further, one aspect of the present invention relates to a method for manufacturing the semiconductor device using a coating process.

An organic semiconductor film can be formed by dissolving an organic semiconductor compound in a solvent and applying the obtained solution. While a vacuum process is required to form an inorganic semiconductor film made of silicon or the like, an organic semiconductor film can be formed without using such a vacuum process. Therefore, its manufacturing cost is relatively low. Further, since it is not necessary to reduce the pressure in the chamber where the film is formed to vacuum, it is relatively easy to form the organic semiconductor film in the large chamber. In this case, it is possible to manufacture a semiconductor element including an organic semiconductor film in a large area and in a large amount. In addition, the organic semiconductor film is formed without using the high temperature heating process required for forming the inorganic semiconductor film. Therefore, the substrate on which the organic semiconductor film is formed is not limited to the heat-resistant substrate, and may be a flexible substrate made of a relatively inexpensive plastic material. As a result, it is now possible to manufacture flexible devices, which was difficult when using a semiconductor element containing an inorganic semiconductor film. Under such circumstances, research and development of semiconductor devices including organic semiconductor films and devices including them have been actively carried out.

An example of a semiconductor device containing an organic semiconductor film is a thin film transistor in which a channel is formed in the organic semiconductor film. For the practical use of such a transistor, its manufacturing process (for example, a technique of selectively applying an organic semiconductor layer only to a part that functions as a channel) and characteristics (for example, high carrier mobility, from on to off). It is important to establish that hysteresis does not occur (hysteresis-free) and the drain current changes abruptly in the vicinity of the threshold voltage) during switching of the above or vice versa.

In the thin film transistor, the gate electrode film and the semiconductor film are arranged so as to overlap with each other via the gate insulating film. In general, a structure in which a semiconductor film is arranged on a gate electrode film via a gate insulating film (bottom gate type structure) is often adopted. Then, depending on the voltage applied to the gate electrode film, it is determined whether or not the carrier channel is formed in the region near the gate insulating film of the semiconductor film. Here, the carrier conduction in the organic semiconductor film included in the thin film transistor is strongly influenced by the physical and chemical properties of the gate insulating film at the interface with the organic semiconductor film.

For example, Patent Document 1 _{discloses that when SiO 2} is used as the gate insulating film, the hydroxyl groups, oxygen and water existing on the surface thereof serve as trap sites for carrier conduction. As a means for improving the surface of such a gate insulating film, for example, Non-Patent Document 1 discloses that a treatment (SAM treatment) for forming a self-assembled monolayer at the interface of the gate insulating film is effective. ing. Further, in Non-Patent Document 2, an organic thin film transistor using a highly water-repellent fluororesin (Cytop (registered trademark)) as a gate insulating film and a rubrene single crystal as an organic semiconductor film is hysteresis-free and remarkably. It is disclosed that it exhibits steep switching characteristics. However, the surface of such a gate insulating film has extremely high liquid repellency with respect to the organic semiconductor film. Therefore, the patterning of the organic semiconductor film on such a gate insulating film is performed through a complicated process described later.

As a technique for patterning an organic semiconductor film, for example, a method using a repulsion pattern and a method using a bank are known.

As a method of using the repellent pattern, a method of patterning by various means after applying SAM treatment to the interface of the gate insulating film is known. For example, Patent Document 1 and Non-Patent Document 3 disclose that the entire surface of the gate insulating film is subjected to SAM treatment, and then the portion other than the portion that becomes the channel forming region is liquefied by exposure treatment. As a result, it is possible to prevent the solution containing the material constituting the applied organic semiconductor film as a solute from being repelled at the portion where the exposure treatment is performed. Further, the organic semiconductor film can be left without being repelled even in a portion surrounded by the exposed portion. On the other hand, Non-Patent Document 4 discloses that the entire surface of the gate insulating film is subjected to SAM treatment, and then only a portion that becomes a channel forming region is liquefied by exposure treatment. Thereby, it is possible to apply the solution containing the material constituting the organic semiconductor film as a solute only to the portion where the exposure treatment has been performed. Further, in Patent Document 2, a method of forming a repellent pattern utilizing a change in the density of a self-assembled monolayer and applying a solution containing a material constituting an organic semiconductor film as a solute is applied only to the parent liquid portion. It is shown.

Further, as a method of using a bank, a bank is formed by using a photolithography process, and the organic semiconductor film is positioned at a desired position by inhibiting the flow of a solution containing a material constituting the organic semiconductor film as a solute. There is a known method of forming a film. For example, Non-Patent Document 5 discloses that a fluororesin is used as the process bank.

Japanese Unexamined Patent Publication No. 2009-60032 Japanese Unexamined Patent Publication No. 2008-192724

One aspect of the present invention is to provide a semiconductor device including a thin film transistor that can be manufactured more easily than a conventional method.

Prior to the formation of the organic semiconductor film on the insulating film having liquid repellency against the solvent which is the main component of the solution containing the material constituting the organic semiconductor film as a solute, the present inventors have a parent for the solvent. It has been found that the organic semiconductor film can be formed at a desired position, for example, in a channel forming region of a transistor by forming a film having a liquid conductive film in a desired shape.

That is, in the semiconductor device of one aspect of the present invention, the conductive film that functions as a source and drain in the layer above the insulating film that functions as the gate insulating film and under the organic semiconductor film has a desired shape. It is a gist that a conductive film having a desired shape is provided separately from the conductive film that functions as a source and a drain. Further, in the method for manufacturing a semiconductor device according to one aspect of the present invention, a conductive film that functions as a source and a drain is desired in a layer above the insulating film that functions as a gate insulating film and under the organic semiconductor film. The gist is to form a film into a shape, or to form a conductive film having a desired shape separately from the conductive film that functions as a source and a drain.

For example, the first conductive film, the insulating film on the first conductive film, the second conductive film and the third conductive film on the insulating film, and the organic semiconductor film on the insulating film, the second conductive film and the third conductive film. The second conductive film includes a portion extending along the first direction, and the third conductive film includes a first portion located in the first direction and a second conductive film as viewed from the second conductive film. The second portion located in the second direction orthogonal to the first direction and the third portion located in the third direction opposite to the second direction when viewed from the region between the conductive film and the first portion, and the third portion. The first part, 2 At least a part of the portion and at least a part of the third portion extend continuously, and the surface free energy of the insulating film is smaller than the surface free energy of the second conductive film and the surface free energy of the third conductive film. The semiconductor device is one aspect of the present invention.

Further, a step of forming a first conductive film, a step of forming an insulating film on the first conductive film, and a step of irradiating the first region and the second region of the insulating film with ultraviolet rays are described. It includes a step of forming a second conductive film and a third conductive film in each of the first region and the second conductive film, and a step of forming an organic semiconductor film on the insulating film, the second conductive film and the third conductive film, respectively. The first region extends along the first direction, and the second region is from the first portion located in the first direction when viewed from the first region and the region between the first region and the first portion. Seen, the second part located in the second direction orthogonal to the first direction, the third part located in the third direction opposite to the second direction, and the opposite of the first direction when viewed from the second part. Includes a fourth portion located in the fourth direction, which is the direction, and a fifth portion located in the fourth direction when viewed from the third portion, and includes at least a part of the first portion, the second portion, and the third portion. At least a part of the contact angle of the solvent, which is the main component of the solution containing the material constituting the organic semiconductor film as a solute, with respect to the gate insulating film is determined by the second conductive film and the third conductive film of the solvent. A method for manufacturing a semiconductor device, which includes a step of forming an organic semiconductor film having a contact angle larger than the contact angle with respect to each of the films and a step of applying a solution along a fourth direction, is also an aspect of the present invention.

In one aspect of the present invention, it is possible to provide a thin film transistor having an organic semiconductor film without going through complicated steps such as a method using a conventional repellent pattern and a method using a bank.

The top view which shows an example of the semiconductor device of one aspect of this invention. FIG. 2 is a cross-sectional view taken along the line AA'shown in FIG. 1A. Top view showing a state in which the organic semiconductor film 7 is removed from the semiconductor device shown in FIG. 1A. The top view which shows an example of the semiconductor device of one aspect of this invention. FIG. 3A is a cross-sectional view taken along the line BB'shown in FIG. 3A. Top view showing a state in which the organic semiconductor film 25 is removed from the semiconductor device shown in FIG. 3A. The cross-sectional view which shows an example of the manufacturing method of the semiconductor device of one aspect of this invention. The cross-sectional view which shows an example of the manufacturing method of the semiconductor device of one aspect of this invention. The cross-sectional view which shows an example of the manufacturing method of the semiconductor device of one aspect of this invention. The cross-sectional view which shows an example of the manufacturing method of the semiconductor device of one aspect of this invention. FIG. 5 is a side view showing an example of a method of applying a solution containing a material constituting the gate electrode film 15 as a solute. The top view which shows an example of the coating method of the solution containing the material constituting the organic semiconductor film 25 as a solute. FIG. 6 is a cross-sectional view taken along the line CC'shown in FIG. 7A. The top view which shows an example of the coating method of the solution containing the material constituting the organic semiconductor film 25 as a solute. FIG. 6 is a cross-sectional view taken along the line CC'shown in FIG. 8A. The top view which shows an example of the coating method of the solution containing the material constituting the organic semiconductor film 25 as a solute. FIG. 9 is a cross-sectional view taken along the line CC'shown in FIG. 9A. The top view which shows an example of the coating method of the solution containing the material constituting the organic semiconductor film 25 as a solute. FIG. 4 is a cross-sectional view taken along the line CC'shown in FIG. 10A. The top view which shows an example of the coating method of the solution containing the material constituting the organic semiconductor film 25 as a solute. FIG. 4 is a cross-sectional view taken along the line CC'shown in FIG. 10A. The cross-sectional view which shows the modification example of the semiconductor device. Top view showing a modification example of a conductive film in which an organic semiconductor film is first formed in a semiconductor device. Top view showing a modification example of a conductive film in which an organic semiconductor film is first formed in a semiconductor device. Top view showing a conductive example in which an organic semiconductor film is first formed in a semiconductor device. A polarizing microscope photograph of the semiconductor device obtained in Example 1. The figure which shows the output characteristic of the organic thin film transistor element included in the semiconductor device obtained by Example 1. FIG. The figure which shows the transmission characteristic of the organic thin film transistor element included in the semiconductor device obtained by Example 1. FIG. A polarizing microscope photograph of the semiconductor device obtained in Example 3. The figure which shows the output characteristic of the organic thin film transistor element included in the semiconductor apparatus obtained in Example 3. FIG. The figure which shows the transmission characteristic of the organic thin film transistor element included in the semiconductor device obtained in Example 3. FIG. A polarizing microscope photograph of the semiconductor device obtained in Example 6. A polarizing microscope photograph of the semiconductor device obtained in Example 8. A polarizing micrograph showing a semiconductor film obtained in Example 10. A polarizing microscope photograph of the semiconductor device obtained in Example 11. A polarizing microscope photograph of the semiconductor device obtained in Example 13. A polarizing microscope photograph of the semiconductor device obtained in Example 15. A polarizing microscope photograph of the semiconductor device obtained in Example 16. A polarizing microscope photograph of the semiconductor device obtained in Example 17. A polarizing micrograph of a semiconductor device obtained in Comparative Example 1.

1 Example of a semiconductor device (1) An example of a case where a conductive film functioning as a source and a drain has a desired shape with respect to a structure FIGS. 1A and 1B are diagrams showing an example of a semiconductor device according to an aspect of the present invention. Specifically, FIG. 1A is a top view of the semiconductor device, and FIG. 1B is a cross-sectional view taken along the line segment AA'of FIG. 1A. Further, FIG. 2 is a top view showing a state in which the organic semiconductor film 7 is removed from the semiconductor device shown in FIG. 1A.

The semiconductor device shown in FIGS. 1A and 1B includes a substrate 1, a base film 2 on the substrate 1, a conductive film 3 on the base film 2, an insulating film 4 on the conductive film 3, and a conductor on the insulating film 4. The film 5 and the conductive film 6 and the insulating film 4, the conductive film 5 and the organic semiconductor film 7 on the conductive film 6 are included. Then, the semiconductor device functions as a transistor. Specifically, the conductive film 3 functions as a gate, the conductive film 5 functions as one of the source and the drain, and the conductive film 6 functions as the other of the source and the drain.

The

conductive films

5 and 6 are arranged separately from each other in the layer on the insulating film 4 and under the organic semiconductor film 7. The conductive film 5 includes a portion extending from left to right on the paper surface of FIGS. 1A and 2. Further, the conductive film 6 extends so as to surround the right end of the conductive film 5 on the paper surface of FIGS. 1A and 2. In other words, the conductive film 5 extends along the first direction, and the conductive film 6 has a first portion 6-1 located in the first direction as viewed from the conductive film 5, and the conductive film 5 and the first. The second portion 6-2 located in the second direction orthogonal to the first direction and the third located in the third direction opposite to the second direction when viewed from the region 8-1 between the portions 6-1. The fourth part 6-3 and the third part 6-3, which are located in the fourth direction opposite to the first direction when viewed from the second part 6-3 and the second part 6-2. Includes a fifth portion 6-5 located in the direction.

Further, the shape of the conductive film 6 shown in FIGS. 1A and 2 can be expressed as a "U" shape. Specifically, the conductive film 6 extends in the direction in which the conductive film 5 extends, that is, the upper portion and the lower portion extending along the first and fourth directions described above, and the conductive film 5 extends. It consists of a direction orthogonal to the direction, that is, an intermediate portion extending along the second and third directions described above. Then, typically, the end on the first direction side of the upper portion and the end on the second direction side of the intermediate portion are continuous, and the end on the first direction side of the lower portion and the end on the third direction side of the intermediate portion. The ends are continuous. However, as long as there is no problem in forming the organic semiconductor film 6 described later, the end on the first direction side of the upper portion and the end on the second direction side of the intermediate portion do not necessarily have to be continuous, and between these ends. There can be some space. Similarly, with respect to the end on the first direction side of the lower portion and the end on the third direction side of the intermediate portion, these ends do not necessarily have to be continuous as long as the film formation of the organic semiconductor film described later is not hindered. There can also be some space between the ends. The intermediate portion includes the first portion 6-1 shown in FIGS. 1A and 2. The upper portion also includes a second portion 6-2 and a fourth portion 6-4 shown in FIGS. 1A and 2. The lower portion also includes the third portion 6-3 and the fifth portion 6-5 shown in FIGS. 1A and 2. The conductive film 6 is arranged so that at least a part of the conductive film 5 is located between the upper portion and the lower portion.

B. Example of a case where a conductive film having a desired shape is provided in addition to the conductive film functioning as a source and a drain. FIGS. 3A and 3B are diagrams showing another example of the semiconductor device according to one aspect of the present invention. .. Specifically, FIG. 3A is a top view of the semiconductor device, and FIG. 3B is a cross-sectional view taken along the line segment BB'of FIG. 3A. Further, FIG. 4 is a top view showing a state in which the organic semiconductor film 25 is removed from the semiconductor device shown in FIG. 3A.

The semiconductor device shown in FIGS. 3A and 3B includes a base 11, a base film 13 on the base 11, a conductive film 15 on the base film 13, an insulating film 17 on the conductive film 15, and a conductive film on the insulating film 17. It includes

films

19, 21 and 23, and an insulating film 17 and an organic semiconductor film 25 on the

conductive films

19, 21 and 23. Then, the semiconductor device functions as a transistor. Specifically, the conductive film 15 functions as a gate, the conductive film 19 functions as one of the source and the drain, and the conductive film 21 functions as the other of the source and the drain.

The

conductive films

19, 21 and 23 are arranged separately from each other in the layer on the insulating film 17 and under the organic semiconductor film 25. The

conductive films

19 and 21 include portions extending substantially in parallel from left to right on the paper surface of FIGS. 3A and 4. Further, the conductive film 23 extends so as to surround the right end of the

conductive films

19 and 21 on the paper surface of FIGS. 3A and 4. In other words, the

conductive films

19 and 21 extend substantially in parallel along the first direction, and the conductive film 23 is the first portion 23-1 located in the first direction when viewed from the

conductive films

19 and 21. , In the direction opposite to the second portion 23-2 and the second direction located in the second direction orthogonal to the first direction, as viewed from the region 30-1 between the

conductive films

19 and 21 and the first portion 23-1. A third part 23-3 located in a certain third direction, a fourth part 23-4 located in the fourth direction opposite to the first direction when viewed from the second part 23-2, and a third part. Includes a fifth portion 23-5 located in the fourth direction as viewed from 23-3.

Further, the shape of the conductive film 23 shown in FIGS. 3A and 4 can be expressed as a "U" shape like the conductive film 6 shown in FIGS. 1A and 2.

C. Structural features of semiconductor devices In the semiconductor devices shown in FIGS. 1A and 1B and 3A and 3B, the insulating

films

4 and 17 are the main components of a solution containing the materials constituting the

organic semiconductor films

7 and 25 as solutes. An insulating film having a liquid-repellent property to a certain solvent is applied, and a conductive film having a liquid-similar property to the solvent is applied as the

conductive films

5, 6, 19 and 21 and the conductive film 23 which function as a source and a drain. ing. That is, the surface free energy of the insulating

films

4 and 17 is smaller than the surface free energy of the

conductive films

5, 6, 19, 21 and 23. Therefore, the contact angle of the solvent with respect to the insulating

films

4 and 17 is larger than the contact angle of the solvent with respect to the

conductive films

5, 6, 19, 21 and 23, respectively.

The shapes of the

conductive films

6 and 23 are not limited to the shapes shown in FIGS. 1A, 2, 3A and 4. However, the insulating film 4 in the region between the conductive film 5 and the conductive film 6 (see FIGS. 1A and 2) or the region between the conductive film 19 and the conductive film 21 (see FIGS. 3A and 4), which is the channel forming region of the thin film transistor. Alternatively, in order to form the

organic semiconductor film

7 or 25 on 17, it is necessary to form a film having the following shape.

First, in the film forming process of the

organic semiconductor film

7 or 25 described later, the solution containing the material constituting the

organic semiconductor film

7 or 25 as a solute is prepared from right to left on the papers of FIGS. 1A, 2, 3A and 4. It is applied towards, i.e., along the fourth direction described above. As described above, the insulating

films

4 and 17 have liquid repellency to the solvent which is the main component of the solution, and the

conductive films

6 and 23 have liquor property to the solvent. It will be started when the

conductive films

6 and 23 come into contact with the solution. In the present specification, the start of coating means that the solution to be coated begins to remain on the object to be coated separately and independently from the coating members such as blades and rollers. Then, the solution is applied to a region between the conductive film 5 and the conductive film 6 (see FIGS. 1A and 2) or a region between the conductive film 19 and the conductive film 21 (FIGS. 3A and 4), which is a channel forming region of the thin film transistor. It must be started before the insulating

film

4 or 17 in (see) comes into contact with the solution. Therefore, the conductive film 6 needs to be formed into a shape including the portion existing in the first direction (for example, the first portion 6-1) when viewed from the conductive film 5. Similarly, the conductive film 23 needs to be formed into a shape including the portion existing in the first direction (for example, the first portion 23-1) when viewed from the conductive film 19 and the conductive film 21. be.

Further, in the film forming process of the

organic semiconductor films

7 and 25 described later, the material constituting the

organic semiconductor films

7 and 25 contained as a solute in the solution is placed between the conductive film 5 and the conductive film 6 in the coating direction thereof. Precipitated in the region (region 8-1 shown in FIGS. 1A and 2) or the region between the

conductive films

19 and 21 in the coating direction thereof and the conductive film 23 (region 30-1 shown in FIGS. 3A and 4). Need to remain. In other words, in the manufacturing process, it is prevented that the solution is repelled from the regions 6-1 and 30-1 in the direction orthogonal to the direction in which the solution is applied, that is, in the above-mentioned second and third directions. There is a need to. Therefore, the conductive film 6 includes the portions (for example, the second portion 6-2 and the third portion 6-3) existing in the above-mentioned second direction and the third direction when viewed from the region 8-1. It is necessary to form a film so that at least a part of the portion extends continuously from the portion existing in the first direction (for example, the first portion 6-1). Similarly, the conductive film 23 includes portions (for example, second portion 23-2 and third portion 23-3) existing in the above-mentioned second and third directions when viewed from the region 30-1. It is necessary to form a film so that at least a part of the portion extends continuously from the portion existing in the first direction (for example, the first portion 23-1).

Similarly, in the film forming process of the

organic semiconductor films

7 and 25 described later, the conductive film 5 and the conductive film 6 in a direction in which the materials constituting the

organic semiconductor films

7 and 25 contained as solutes in the solution are orthogonal to the coating direction thereof. In the region between (regions 8-2 and 8-3 shown in FIGS. 1A and 2), or in the region between the conductive film 19 and the conductive film 23 in the direction orthogonal to the coating direction thereof (in FIGS. 3A and 4). It is necessary to remain to some extent in the indicated region 30-2) and the region between the conductive film 21 and the conductive film 23 (region 30-3 shown in FIGS. 3A and 4). In other words, in the film forming process, the solution is repelled from the regions 6-1 and 6-2, 30-1 and the region 30-2 in the direction in which the solution is applied, that is, in the fourth direction described above. Need to be prevented. Therefore, the conductive film 6 is formed into a shape including a portion (for example, a fourth portion 6-4 and a fifth portion 6-5) that overlaps with the conductive film 5 in the above-mentioned second and third directions. Need to be done. Similarly, the conductive film 23 has a shape that includes portions (for example, fourth portion 23-4 and fifth portion 23-5) that overlap with the

conductive films

19 and 21 in the second and third directions described above. Needs to be filmed.

Although not shown in FIGS. 1A, 1B, and 2, the

conductive films

3, 5 and 6 are electrically connected to other circuit elements (transistors, signal lines, power supply lines, etc.). Similarly, although not shown in FIGS. 3A, 3B and 4, the

conductive films

15, 19 and 21 are electrically connected to other circuit elements. On the other hand, the conductive film 23 shown in FIGS. 3A, 3B and 4 is not connected to other circuit elements, that is, is electrically isolated.

(2) Materials A. Bases 1 and 11
As the

substrates

1 and 11, low heat resistant plastic substrates such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET) or polypropylene, or highly heat resistant plastic substrates such as polycarbonate, silicon substrates, glass substrates and the like are applied. Can be done. When a flexible substrate such as a plastic substrate is applied as the

substrates

1 and 11, it is preferable because the entire semiconductor device can be made flexible. Further, as the

substrates

1 and 11, pulp substrates impregnated with a fluororesin may be applied.

B. Undercoat films

2 and 13 and insulating

films

4 and 17
The

base films

2 and 13 and the insulating

films

4 and 17 may contain a fluororesin. Further, the

base films

2 and 13 and the insulating

films

4 and 17 may be made of a fluororesin. The surfaces of the

base films

2 and 13 and the insulating

films

4 and 17 are preferably smooth surfaces without irregularities. Further, the

undercoat films

2 and 13 and the insulating

films

4 and 17 in one aspect of the present invention need to generate photochemical reaction radicals by irradiating with ultraviolet rays (details will be described later). Therefore, it is preferable to apply a polymer insulating material such as a fluororesin that generates reactive radicals as the

base films

2 and 13 and the insulating

films

4 and 17.

Examples of the fluororesin include polychlorotrifluoroethylene, polyvinylfluoride, ethylene-chlorotrifluoroethylene copolymer, polyvinylidene fluoride, perfluoroethylene propene copolymer, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, and the like. Examples thereof include perfluoroalkoxyalkane and a fluororesin having a perfluoroalkyl ether ring structure.

Further, it is more preferable to use a perfluoro resin, particularly a fluororesin having a perfluoroalkyl ether ring structure, as the

undercoat films

2 and 13 and the insulating

films

4 and 17. This is because a transistor having excellent characteristics can be obtained. For example, a perfluoro (3 butenyl vinyl ether) polymer (CYTOP (registered trademark) manufactured by AGC) or a perfluorodimethyldioxol-tetrafluoroethylene copolymer (Teflon (registered trademark) AF) may be used as the base film 2. And 13 and the materials applied to the insulating

films

4 and 17 are particularly preferable.

C. Conductive films

3, 5, 6, 15, 19, 21 and 23
The

conductive films

3, 5, 6, 15, 19, 21 and 23 may contain a metal or an alloy containing the same, a conductive organic substance, or an organic substance in which metal nanoparticles are dispersed. Further, the

conductive films

3, 5, 6, 15, 19, 21 and 23 may be made of a metal or an alloy containing the same, a conductive organic substance, or an organic substance in which metal nanoparticles are dispersed. Further, the

conductive films

5 and 6 shown in FIGS. 1A and 1B and 2 may be made of the same material. Further, the

conductive films

19, 21 and 23 shown in FIGS. 3A and 3B and 4 may be made of the same material. In this case, the

conductive films

5 and 6 or the

conductive films

19, 21 and 23 can be formed at the same time, which is preferable.

Examples of metals contained in

conductive films

3, 5, 6, 15, 19, 21 and 23 or alloys containing them include platinum, gold, silver, aluminum, chromium, tungsten, copper, iron, lead, titanium and indium. And the like and alloys containing them (InО ₂ , ZnO ₂ , and indium tin oxide (ITO), etc.) and the like.

Examples of the conductive organic substances contained in the

conductive films

3, 5, 6, 15, 19, 21 and 23 include conductive polymer compounds such as polythiophene, polyacetylene and polyparaphenylene vinylene, carbon nanotubes and graphene.

Examples of organic substances in which metal nanoparticles contained in

conductive films

3, 5, 6, 15, 19, 21 and 23 are dispersed include tetrachloromethane, benzene, dichlorobenzene, dichloromethane, toluene, octane, tetralin and mesitylene. , Butanol, methanol and the like.

Examples of metal nanoparticles dispersed in the organic substance include metal nanoparticles containing gold, silver or copper as a main component and other metal elements. The metal nanoparticles have a size generally called nano size (less than 1 μm), and the average particle size is preferably 10 nm or more and 100 nm or less, more preferably 30 nm or less. Further, when the metal nanoparticles contain gold or silver, the conductivity of the obtained electrode film is high, which is preferable.

Further, the ratio of the metal nanoparticles is preferably 30% or more and 60% or less in terms of weight% with respect to the total mass of the material. As a result, when the thicknesses of the

conductive films

3, 5, 6, 15, 19, 21 and 23 are set in a suitable range (range of 15 to 100 nm, particularly in the range of 30 to 90 nm), these can be produced in a desired pattern. It becomes easy to film.

Further, the metal nanoparticles may be coated with an organic molecular layer containing an alkylamine, an alkyldiamine, or an amine having another structure. It is considered that this coated portion is formed by bonding a large number of alkylamine molecules to metal nanoparticles by coordination bonds of amino groups and aggregating the alkyl group portions on the surface of the metal nanoparticles. Therefore, the weight ratio of the coated portion can be adjusted by adjusting the molecular weight of the alkylamine mainly used.

Examples of organic molecular layers containing alkylamines, alkyldiamines, or amines having other structures that coat metal nanoparticles include the following.

First, medium- and short-chain alkylamines are not particularly limited in their structure, but are RNH ₂ _{(R is a hydrocarbon chain) which is a primary amino group or R 1} R ₂ NH (R ₁ , R) which is a secondary amino group. ₂ is a hydrocarbon chain and may be the same or different). Further, the medium- and short-chain alkylamine has a boiling point of 100 ° C. or higher in consideration of the thermal decomposition temperature of the complex compound, and 250 ° C. or lower in consideration of the low-temperature sinterability of the coated metal nanoparticles. Is considered to be the boiling point of. For example, 2-ethoxyethylamine, dipropylamine, dibutylamine, hexylamine, cyclohexylamine, heptylamine, 3-butoxypropylamine, octylamine, nonylamine, decylamine, 3-aminopropyltriethoxysilane, dodecylamine and the like can be mentioned. However, it is not limited to these.

Examples of long-chain and medium-chain alkylamines include dipropylamine, dibutylamine, hexylamine, cyclohexylamine, heptylamine, 3-butoxypropylamine, octylamine, nonylamine, decylamine, 3-aminopropyltriethoxysilane, and the like. Alkyl amines such as dodecylamine, hexadecylamine, oleylamine, and octadecylamine. Any long-chain or medium-chain alkylamine having 6 or more carbon atoms can be appropriately used depending on the intended purpose.

Examples of the short-chain alkylamine include amylamine, 2-ethoxyethylamine, 4-methoxybutylamine, diisopropylamine, butylamine, diethylamine, propylamine, isopropylamine, ethylamine, dimethylamine and the like.

The structure of the medium- and short-chain alkyldiamine is not particularly limited, but at least one amino group is RNH ₂ (R is a hydrocarbon chain) or a secondary amino group, R ₁ R _2. It is desirable that it is NH (R ₁ and R ₂ may be the same or different in the hydrocarbon chain). The medium- and short-chain alkyldiamine has a boiling point of 100 ° C. or higher in consideration of the thermal decomposition temperature of the complex compound, and a boiling point of 250 ° C. or lower in consideration of the low-temperature sinterability of the coated metal nanoparticles. Is considered. For example, ethylenediamine, N, N-dimethylethylenediamine, N, N'-dimethylethylenediamine, N, N-diethylethylenediamine, N, N'-diethylethylenediamine, 1,3-propanediamine, 2,2-dimethyl-1,3. -Propane diamine, N, N-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N-diethyl-1,3-diaminopropane, 1,4-diaminobutane , 1,5-Diamino-2-methylpentane, 1,6-diaminohexane, N, N'-dimethyl-1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane and the like. However, it is not limited to these.

D.

Organic semiconductor films

7 and 25
The

organic semiconductor films

7 and 25 may include one or both of a high molecular weight organic semiconductor material and a low molecular weight organic semiconductor material. In the present specification, the polymer means a molecule having a molecular weight of more than 10,000, and the small molecule means a molecule having a molecular weight of 10,000 or less. The organic semiconductor material constituting the

organic semiconductor films

7 and 25 is preferably a small molecule organic semiconductor material. Further, the molecular weight of the small molecule organic semiconductor material is preferably 1500 or less, more preferably 800 or less. The molecular skeleton of the organic semiconductor material is not particularly limited as long as it has semiconductor performance.

As the low molecular weight organic semiconductor material constituting the

organic semiconductor films

7 and 25, a condensed polycyclic aromatic compound is preferable, a condensed polycyclic aromatic compound having an acene skeleton or a heteroacene skeleton is more preferable, and a condensed polycyclic having a thienoacene skeleton is more preferable. Aromatic compounds are particularly preferable, and compounds represented by the following formula (2) or (3) are most preferable. Further, since the organic semiconductor material is dissolved in an organic solvent when the

organic semiconductor films

7 and 25 are formed, it is preferable that the organic semiconductor material has solvent solubility. For example, it is preferable that the organic semiconductor material has an alkyl group in order to ensure solubility. The thienoacene skeleton refers to a compound containing at least one thiophene ring structure represented by the following formula (1) as a condensed ring site in the molecular structure.

In formula (2), R1 represents an alkyl group. Further, R2 represents an aromatic hydrocarbon group which may have an alkyl group or a heterocyclic group which may have an alkyl group. Further, in the formula (3), when R3 and R5 are hydrogen atoms, one of R4 and R6 has an alkyl group, and the other has an aromatic hydrocarbon group or an alkyl group which may have an alkyl group. Represents a optionally heterocyclic group. Further, in the formula (3), when any three of R3 to R6 are hydrogen atoms, the remaining one represents an alkyl group.

These alkyl groups are not limited to straight chain, branched chain and cyclic. For example, examples of these alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group and n-. Dodecyl group, 2-ethylhexyl group and the like can be mentioned. As these alkyl groups, a linear alkyl group is preferable, a linear alkyl group having 4 to 14 carbon atoms is more preferable, a linear alkyl group having 6 to 12 carbon atoms is further preferable, and a linear alkyl group having 8 to 12 carbon atoms is more preferable. A straight chain alkyl group is most preferred.

The aromatic hydrocarbon group which may have an alkyl group means a functional group in which one of the hydrogen atoms on the aromatic hydrocarbon is substituted with an alkyl group, and specific examples thereof include a phenyl group and a naphthyl group. , Anthrill group and the like. As the aromatic hydrocarbon group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

The heterocyclic group which may have an alkyl group represents a similar mode in which the aromatic hydrocarbon group is replaced with the heterocyclic group. Examples of the heterocyclic group include a pyridyl group, a pyrazil group, a pyrimidyl group, an imidazolyl group, a thienyl group, a benzothienyl group and the like. In addition, a preferable heterocyclic group includes a thienyl group or a benzothienyl group.

Examples of the polymer organic semiconductor material constituting the

organic semiconductor films

7 and 25 include polythiophene, polyphenylene vinylene, polyfluorene, polyacetylene, polypyrrole, etc., as well as monomers having high electron density such as benzodithiophene and thienothiophene, and benzothiasiasol. , Benzobistianiazole, diketopyrrolopyrrole and other donor-acceptor-type polymers obtained by copolymerizing monomers with low electron density.

Two or more materials may be mixed and used as an organic semiconductor material constituting the

organic semiconductor films

7 and 25 for the purpose of improving the characteristics of the semiconductor device or imparting other characteristics. The organic semiconductor material to be mixed may be either a high molecular weight organic semiconductor material or a low molecular weight organic semiconductor material. Generally, the higher the crystallinity of the semiconductor film, the better the characteristics of the thin film transistor. For example, Adv. Mater. 2018.30.1072756 describes that an organic semiconductor film having high crystallinity can be obtained by using a mixture of two kinds of small molecule organic semiconductor materials. Therefore, when the

organic semiconductor films

7 and 25 are formed using an organic semiconductor material in which two or more materials are mixed, it is preferable that both of the two materials are low molecule organic semiconductor materials. Further, it is more preferable that the two materials are small molecule organic semiconductors having the same molecular structure and different alkyl group lengths.

Further, these materials may be dispersed in an organic substance as a solvent. That is, the

organic semiconductor films

7 and 25 may be made of an organic substance in which these materials are dispersed. Further, the

organic semiconductor films

7 and 25 may contain additives.

The additives contained in the

organic semiconductor films

7 and 25 are not particularly limited as long as they do not interfere with the function of the semiconductor device. For example, examples of such additives include insulating materials, surfactants or thickeners for rheology control, carrier injection or dopants for adjusting the amount of carriers, and the like.

The organic substance that serves as a solvent for these materials can be used without particular limitation as long as it can dissolve and disperse these materials, but when storage stability is taken into consideration, it must be a solvent that can dissolve the materials. Is desirable. Examples of the organic substances include halogen-based solvents such as chloroform, chlorobenzene and dichlorobenzene, aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, mesitylene, tetraline and cyclohexylbenzene, and ethers such as tetrahydrofuran, anisole and phenetol. Amids such as dimethylformamide and dimethylacetamide, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone, esters such as methyl benzoate and ethyl benzoate, and hydrocarbons such as cyclohexane and decalin Can be mentioned.

2 Example of Manufacturing Method of Semiconductor Device FIGS. 5A to 5D are diagrams showing an example of the manufacturing method of the semiconductor device shown in FIGS. 1A, 1B and 2, and specifically, the base film 2 is manufactured on the substrate 1. It is a figure which shows from the film (FIG. 5A) to the film formation of the conductive film 5 and 6 (FIG. 5D) in the order of film formation. Although FIGS. 5A to 5D show an example of a method for manufacturing the semiconductor device shown in FIGS. 1A, 1B and 2, the semiconductor device shown in FIGS. 3A, 3B and 4 can be manufactured by the same manufacturing method. Is also possible.

First, a solution containing the material constituting the base film 2 as a solute is applied onto the substrate 1. As a method for applying the solution, a spin coating method, a dip coating method, a spray coating method, a droplet ejection method, a die coating method and the like can be applied. When the base film 2 is applied to the entire upper surface of the flat plate-shaped substrate 1, it is preferable to apply spin coating. Then, the applied solution may be heat-treated at a temperature of 200 ° C. or lower, or may be naturally dried. As a result, the formation of the base film 2 on the substrate 1 is completed (see FIG. 5A).

Next, the base film 2 in the region where the conductive film 3 is later formed (first pattern region) is selectively irradiated with ultraviolet rays. As a method of irradiating ultraviolet rays, a method of irradiating the entire surface of the base film 2 with ultraviolet rays while covering a region other than the first pattern region with a photomask, a method of irradiating only the first pattern region with an ultraviolet laser, and the like can be applied. can.

As a result, the surface of the base film 2 in the first pattern region becomes a reactive surface by a photochemical reaction. In the present specification, the reactive surface means that radical groups are generated on the insulating film surface by a photochemical reaction of an insulating film such as a perfluoro resin due to ultraviolet irradiation, and organic substances in which metal nanoparticles are dispersed adhere and aggregate. A surface that is in an easy-to-use state. When the metal nanoparticles are coated with an organic molecular layer containing an alkylamine, an alkyldiamine or an amine having another structure, the radical group promotes the detachment of the organic molecular layer and the metal nanoparticles adhere to each other.・ Aggregation (fusion / aggregation) is promoted. In addition, in this specification, adhesion / agglutination or fusion / aggregation means a state in which metal nanoparticles are adhered (fused) to a film to be formed and aggregated.

The ultraviolet rays irradiated to the base film 2 are irradiated for the purpose of dissociating the bond between carbon (C) and fluorine (F) in the base film 2. The binding energy of carbon (C) and fluorine (F) is about 490 kJ / mol. Therefore, if the wavelength of the ultraviolet rays is 244 nm or less, it is considered that the bond between carbon (C) and fluorine (F) can be dissociated. For example, the wavelength of the ultraviolet rays may be 10 nm to 244 nm, preferably 10 nm to 200 nm, and more preferably 100 nm to 200 nm.

Next, a solution containing the material constituting the conductive film 3 as a solute is applied onto the undercoat film 2. As a method of applying the solution, a method using an application member such as a blade and a roller can be applied. For example, a method of dropping the solution onto the base film 2 and applying the solution to the first pattern region of the base film 2 by sweeping a blade close to the base film 2 or rotating a roller can be applied. .. For example, as shown in FIG. 6, the solution 150 is dropped onto the base film 2, and the blade 200 adjacent to the base film 2 is swept from right to left on the paper surface to bring the solution 150 to the base film 13. It may be applied to one pattern area. The direction in which the blade 200 is swept may be any direction.

As a result, a solution containing the material constituting the conductive film 3 as a solute is applied only to the first pattern region. Then, the applied solution may be heat-treated at a temperature of 200 ° C. or lower, or may be naturally dried. With the above, the film formation of the conductive film 3 is completed (see FIG. 5B). Regarding the formation of the conductive film 3 on the base film 2, the disclosure contents of JP-A-2014-195794 may be referred to.

Next, a solution containing the material constituting the insulating film 4 as a solute is applied onto the base film 2 and the conductive film 3. As a method for applying the solution, the same method as the method for applying the solution containing the material constituting the base film 2 as a solute can be adopted, and therefore the above description is incorporated. Then, the applied solution may be heat-treated at a temperature of 200 ° C. or lower, or may be naturally dried. With the above, the film formation of the insulating film 4 is completed (see FIG. 5C).

Next, the insulating film 4 in the region where the

conductive films

5 and 6 are formed (second pattern region) is selectively irradiated with ultraviolet rays. As the method of irradiating the ultraviolet rays, the same method as the method of irradiating the base film 2 with ultraviolet rays can be adopted, and therefore the above description is incorporated.

Next, a solution containing the materials constituting the

conductive films

5 and 6 as a solute is applied onto the insulating film 4. As a method for applying the solution, the same method as the method for applying the solution containing the material constituting the conductive film 3 as a solute can be adopted, and therefore the above description is incorporated.

As a result, a solution containing the materials constituting the

conductive films

5 and 6 as a solute is applied only to the second pattern region. Then, the applied solution may be heat-treated at a temperature of 200 ° C. or lower, or may be naturally dried. Further, the

conductive films

5 and 6 may be surface-treated. An example of the surface treatment is a surface treatment using benzenethiol in which at least one hydrogen atom is replaced with a fluorine atom. As a result, the change in the work function between the organic semiconductor film 7 to be formed later and the

conductive films

5 and 6 functioning as sources and drains is alleviated, the carrier injection efficiency is improved, and the surface treatment is improved. As a result, the liquid friendliness of the surfaces of the

conductive films

5 and 6 with respect to the solvent which is the main component of the solution containing the material constituting the organic semiconductor film 7 as a solute is improved. With the above, the film formation of the

conductive films

5 and 6 is completed (see FIG. 5D). Regarding the film formation of the

conductive films

5 and 6 on the insulating film 4, the disclosure contents of JP-A-2014-195794 may be referred to.

Next, a solution containing the material constituting the organic semiconductor film 7 as a solute is applied onto the

conductive films

5 and 6 and the insulating film 4. As a method for applying the solution, the same method as the method for applying the solution containing the materials constituting the

conductive films

3, 5 and 6 as a solute can be adopted. However, the application of the solution containing the material constituting the organic semiconductor film 7 as a solute is performed along a specific direction.

An example of a method for applying a solution containing a material constituting the organic semiconductor film 7 as a solute will be described in detail with reference to FIGS. 7A and 7B to 11A and 11B. 7A to 11A are top views showing changes when the solution is applied, and FIGS. 7B to 11B are cross-sectional views taken along the line CC'shown in FIGS. 7A to 11A.

First, a solution 250 containing the material constituting the organic semiconductor film 7 as a solute is dropped onto the insulating film 4 located in the direction opposite to the side where the conductive film 5 is located when viewed from the conductive film 6. Then, as shown in FIGS. 7A and 7B, the blade 300 is placed at a position where it comes into contact with the solution 250 and does not come into contact with the insulating film 4 or the like. The blade 300 preferably has liquid repellency against the solution 250. For example, it is preferable that the surface of the blade 300 is liquid-repellent so as to have liquid-repellent property against the solution 250. As an example of the liquid-repellent treatment on the blade 300, a perfluoro (3 butenyl vinyl ether) polymer (CYTOP (registered trademark) manufactured by AGC Inc.) or a perfluorodimethyldioki, which is a suitable material for the insulating film 4, is used. Processing using a sole-tetrafluoroethylene copolymer (Teflon (registered trademark) AF) or the like can be mentioned. Then, the blade 300 is swept in the direction of the arrow shown in FIG. 7A, that is, from right to left on the paper surface. In other words, the blade 300 is swept along the fourth direction described above.

When the solution 250 also moves to the conductive film 6 side with the movement of the blade 300, the solution 250 is located on the conductive film 6 as shown in FIGS. 8A and 8B. Here, since the conductive film 6 has positivity with respect to the solvent that is the main component of the solution 250, the rear end of the solution 250 (the right end on the paper surface of FIGS. 8A and 8B) follows the movement of the blade 300. It is stretched without. Further, at the rear end of the solution 250, drying (volatilization of the solvent) is promoted. As a result, the organic semiconductor material which is the solute of the solution 250 is precipitated, so that the formation of the organic semiconductor film 7 on the conductive film 6 is started.

As the blade 300 moves further onto the region between the

conductive films

5 and 6 as shown in FIGS. 9A and 9B, the rear portion of the solution 250 (the right portion on the paper in FIGS. 9A and 9B) is already present. It is stretched by the formed organic semiconductor film 7. Further, due to the presence of the conductive film 6 having positivity in the rear and left and right of the rear portion, the rear portion is repelled without being separated from the organic semiconductor film 7 formed on the conductive film 6. It is also located on the liquid insulating film 4. Then, drying (solvent volatilization) is promoted also in the rear portion located in the insulating film 4. As a result, the organic semiconductor material which is the solute of the solution 250 is precipitated, so that the organic semiconductor film 7 is also formed on the conductive film 4. It should be noted that the insulating film 4 on the side opposite to the side where the conductive film 5 is located when viewed from the conductive film 6 does not have a structure for stretching a part of the solution 250, so that the drying of the solution 250 is promoted. Therefore, the organic semiconductor film 7 is not formed.

When the blade 300 further moves onto the region where the conductive film 6 does not exist as shown in FIGS. 10A and 10B, as described above, the organic semiconductor film on the insulating film 4 in the region between the conductive film 5 and the conductive film 6 The film formation of 7 proceeds. However, in the region where the conductive film 6 having positivity does not exist on the left and right of the rear portion of the solution 250, the solution 250 is formed only on the conductive film 5 having positivity and does not overlap with the conductive film 5. The solution 250 in the above moves following the movement of the blade 300.

When the blade 300 further moves onto the region where the conductive film 5 does not exist as shown in FIGS. 11A and 11B, the solution 250 is separated from the organic semiconductor film 7. As a result, the formation of the organic semiconductor film 7 is completed (see FIGS. 1A and 1B).

3 Modification Example The above-mentioned semiconductor device and its manufacturing method are examples of the present invention, and the present invention also includes a semiconductor device having features different from those of the above-mentioned semiconductor device and its manufacturing method and its manufacturing method.

For example, the

base films

2 and 13 shown in FIGS. 1B and 3B are not indispensable configurations in the present invention. Therefore, as shown in FIG. 12, a semiconductor device in which the substrate 1 is in contact with the conductive film 3 and the insulating film 4 is also an aspect of the present invention. Since the semiconductor device shown in FIG. 1B or the like is formed by the above-mentioned manufacturing method, it is preferable in that the conductive film 3 can be patterned with high definition by a relatively simple method. On the other hand, the semiconductor device shown in FIG. 12 is preferable in that the film forming process of the base film 2 can be reduced.

Further, in the semiconductor device of the present invention, the shape of the conductive film on which the organic semiconductor film is first formed (the conductive film 6 shown in FIGS. 1A and 1B and the conductive film 23 shown in FIGS. 3A and 3B) is "co". It is not limited to the shape of. For example, as the shape of the conductive film, any of the shapes of the conductive films 23 ″ to 23 ″ shown in FIGS. 13 to 15 can be applied. Although FIGS. 13 to 15 show modified examples of the conductive film 23 shown in FIGS. 3A and 3B, the shape of the conductive film 7 shown in FIGS. 1A and 1B is shown in FIGS. 13 to 15. It can also be changed to a shape of'~ 23'''.

For example, in the semiconductor device of the present invention, at least a part of the upper surface shape of the conductive film on which the organic semiconductor film is first formed may be curved as in the conductive film 23'shown in FIG. Specifically, the conductive film 23'refers to the direction in which the

conductive films

19 and 21 extend, that is, the upper portion and the lower portion extending along the first direction and the fourth direction, and the upper portion. It consists of an intermediate portion that curves and extends from the end on the unidirectional side to the end on the first direction side of the lower portion.

Further, the conductive film 23'is the same as the conductive film 23 shown in FIGS. 3A and 4, the first portion 23'-1 located in the first direction and the conductive film when viewed from the

conductive films

19 and 21. Seen from the region between 19 and 21 and the first portion 23'-1, the second portion 23'-2 located in the second direction and the third portion 23'-3 located in the third direction described above. And the fourth part 23'-4 located in the fourth direction when viewed from the second part 23'-2, and the fourth part located in the fourth direction when viewed from the third part 23'-3. Includes 5 parts 23'-5 and.

The upper portion of the conductive film 23'includes a part of the second portion 23'-2 and the fourth portion 23'-4. Further, the lower portion of the conductive film 23'includes a part of the third portion 23'-3 and the fifth portion 23'-5. Further, the intermediate portion of the conductive film 23'includes the first portion 23'-1, the rest of the second portion 23'-2, and the third portion 23'-3.

Further, as shown in FIG. 14, the conductive film from which the organic semiconductor film is first formed in the semiconductor device of the present invention may include a plurality of separated sub-conductive films 23A to 23C. Specifically, the sub-conductive film 23A includes the portion 23 ″ -1 located in the first direction as viewed from the

conductive films

19 and 21. Further, the sub-conductive film 23B includes a part located in the second direction when viewed from the region between the

conductive films

19 and 21 and the portion 23''-1, and the above-mentioned first film when viewed from the conductive film 19. It consists of the rest located in two directions. Further, the sub-conductive film 23C is a part located in the third direction when viewed from the region between the

conductive films

19 and 21 and the portion 23 ″ -1, and the above-mentioned first film when viewed from the conductive film 21. It consists of the rest located in three directions. Further, the sub-conductive film 23A is viewed from the portion of the sub-conductive film 23B located in the second direction when viewed from the end of the sub-conductive film 23B on the first direction side and the end of the sub-conductive film 23C on the first direction side. As seen, it includes the portion located in the third direction described above.

Further, the sub-conductive films 23A to 23C shown in FIG. 14 are the first portion 23 located in the first direction described above when viewed from the

conductive films

19 and 21 in the same manner as the conductive films 23 shown in FIGS. 3A and 4. The second portion 23''-2 located in the second direction and the third direction described above when viewed from the region between''-1 and the

conductive films

19 and 21 and the first portion 23''-1. The third part 23''-3 located in the above, the fourth part 23''-4 located in the fourth direction as viewed from the second part 23''-2, and the third part 23''- Seen from 3, the fifth portion 23''-5 located in the fourth direction described above is included.

Note that the first portion 23 ″ -1 in the sub-conductive films 23A to 23C shown in FIG. 14 includes a part of the sub-conductive film 23A. Further, the second portion 23 ″ -2 in the sub-conductors 23A to 23C shown in FIG. 14 includes a part of the sub-conductive film 23A and a part of the sub-conductive film 23B. Here, as shown in FIG. 14, the end of the sub-conductive film 23B extends in the first direction at a position shifted in the third direction (lower part of the figure) from the upper end of the sub-conductive film 23A. Therefore, it is preferable that there is a region where a part of the sub-conductive film 23A and a part of the sub-conductive film 23B overlap in the first direction. Further, the third portion 23 ″ -3 in the sub-conductive film 23A to 23C shown in FIG. 14 includes a part of the sub-conductive film 23A and a part of the sub-conductive film 23C. Here, as shown in FIG. 14, the end of the sub-conductive film 23C extends in the first direction at a position deviated from the lower end of the sub-conductive film 23A in the second direction (upper part of the drawing). Therefore, it is preferable that there is a region where a part of the sub-conductive film 23A and a part of the sub-conductive film 23C overlap in the first direction. Further, the fourth portion 23 ″ -4 in the sub-conductive films 23A to 23C shown in FIG. 14 includes the remainder of the sub-conductive film 23B. Further, the fifth portion 23 ″ -5 in the sub-conductive films 23A to 23C shown in FIG. 14 includes the remainder of the sub-conductive film 23C.

Further, in FIG. 14, an example is shown in which the conductive film from which the organic semiconductor film is first formed is composed of three sub-conductive films 23A to 23C, but the number of sub-conductive films may be 2 or 4 or more. .. In this case, at least one of the first to fifth portions includes at least a part of each of at least two sub-conductives among the plurality of subconductives.

Further, in the semiconductor device of the present invention, the conductive film from which the organic semiconductor film is first formed is one end portion 23 ″ ″ -6 and the other end portion 23, as shown in FIG. '''-7 may extend so as not to overlap with the

conductive films

19 and 21 in the above-mentioned second direction and third direction. The semiconductor device having the conductive film 23 shown in FIG. 4B or the like reduces the parasitic capacitance generated in the

conductive films

19 and 21 as compared with the semiconductor device having the conductive film 23 ′ ″ shown in FIG. It is preferable in that it can be used. On the other hand, the semiconductor device having the conductive film 23'''shown in FIG. 15 has the conductive film 19 and the conductive film which are the channel forming regions of the transistor as compared with the semiconductor device having the conductive film 23 shown in FIG. It is preferable in that the organic semiconductor film 25 can be reliably formed in the region between 21.

Further, in the semiconductor device of the present invention, the

undercoat film

2 or 13 and the

conductive film

3 or 15 may be formed by using a known photolithography step. When the

undercoat film

2 or 13 and the

conductive film

3 or 15 are formed by the above-mentioned film forming method, the

conductive film

3 or 15 can be patterned with high definition by a relatively simple method, which is preferable. On the other hand, when a known photolithography process is used, the degree of freedom in material selection and the like is increased, that is, it is possible to select a material suitable for each from a wider range of options, which is preferable.

Further, in the semiconductor device of the present invention, the

conductive films

5 and 6 or the conductive films 19, the

films

21 and 23 may be formed by the same step or may be formed by different steps. When these are formed in the same process, it is preferable in that the film forming process of the semiconductor device can be reduced. On the other hand, when these are formed by different steps, the degree of freedom in material selection is increased, which is preferable.

Manufacture of a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B A semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B was manufactured . .. First, _{a silicon wafer with a SiO 2} thermal oxide film (100 nm) is prepared as a substrate, and CYTOP CTL809M (registered trademark) manufactured by AGC Inc., which serves as a base film, is spin-coated on the substrate so as to have a thickness of about 25 nm. The film was applied and formed. Next, gold (Au), which is a material for the conductive film, was formed by vapor deposition through a shadow mask so as to have a thickness of 25 nm. The surface of the conductive film was then exposed to vapor of pentafluorobenzenethiol for 20 minutes. Next, No. 1 which is the following known organic semiconductor material. 1 and No. No. 2 was dissolved in chlorobenzene so that the mass concentration was 0.05%, and then No. 1: No. The mixture was mixed at a volume ratio of 2 = 9: 1. .. Next, the obtained solution was blade-coated on the above-mentioned substrate at a rate of 3.5 μm / sec using a glass blade, and dried at room temperature to form an organic semiconductor in which a semiconductor film was formed only where necessary. Manufactured the device. The glass blade is coated with CYTOP CTL809M (registered trademark) manufactured by AGC Inc. The film thickness of the obtained organic semiconductor film was about 5 nm.

FIG. 16 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope. When the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, it was found that the organic semiconductor film was formed on the CYTOP outside the region shown by the dotted line in the figure. No blinking of the indicated color was observed, and it was confirmed that the organic semiconductor film was not formed. On the other hand, in the region surrounded by the conductive film shown by the dotted line, it was confirmed that the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.

Evaluation of Organic Semiconductor Device Described in Example 1 The organic thin film transistor characteristics of an organic thin film transistor element composed of a source electrode and a drain electrode having a channel width of 800 μm and a channel length of 100 μm included in the semiconductor device manufactured in Example 1 were measured. In this organic thin film transistor element, SiO _{2 as} a thermal oxide film layer and CYTOP CTL809M (registered trademark) manufactured by AGC Inc. as an undercoat film serve as an insulating film, and the capacitance is 24 nF / cm ² and the element characteristic value is set. Calculated. The output characteristics of the organic thin film transistor element included in the obtained semiconductor device are shown in FIG. As shown in FIG. 17, the organic thin film transistor element exhibited linear and saturated output characteristics similar to a typical transistor element. Further, as shown in FIG. 18, the thin film transistor was capable of being driven at a low voltage of 2 V or less and had a small hysteresis. When the sub-threshold swing value indicating that the drain current changes abruptly in the vicinity of the threshold voltage was calculated, the value was 67 mV / dec, showing an extremely steep switching characteristic approaching the theoretical limit. Moreover, when the carrier mobility of the organic thin film transistor element was calculated, it showed a high mobility ^{of 4.4 cm 2 / Vs at the maximum.}

Examples except that the shape of the shadow mask required to form a conductive film that functions as a production source and drain of a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 1A and 1B is changed. The semiconductor device was manufactured by the same method as that described in 1. A polarizing microscope photograph of the obtained semiconductor device is shown in FIG. When the location where the organic semiconductor film was formed was confirmed by the same method as that described in Example 1, the organic semiconductor was crystalline only in the region surrounded by the conductive film shown by the dotted line in the figure. The result was that a thin film was obtained.

Evaluation of Organic Semiconductor Device Described in Example 3 The organic thin film transistor characteristics of an organic thin film transistor element composed of a source electrode and a drain electrode having a channel width of 300 μm and a channel length of 50 μm included in the semiconductor device manufactured according to Example 3 were measured. The insulating film and capacitance of the organic thin film transistor element are the same as those of the film and values described in Example 2. The output characteristics of the organic thin film transistor element included in the obtained semiconductor device are shown in FIG. As shown in FIG. 20, the organic thin film transistor element exhibited linear and saturated output characteristics similar to a typical transistor element. Further, as shown in FIG. 21, the thin film transistor was capable of being driven at a low voltage of 2 V or less and had a small hysteresis. When the sub-threshold swing value indicating that the drain current changes abruptly in the vicinity of the threshold voltage was calculated, the value was 75 mV / dec, showing an extremely steep switching characteristic. Moreover, when the carrier mobility of the organic thin film transistor element was calculated, it showed a high mobility ^{of 1.0 cm 2 / Vs at the maximum.}

Evaluation of Variations in Organic Semiconductor Devices Described in Example 1 Characteristics of Organic Thin Film Transistor Elements Consists of Source and Drain Electrodes with a Channel Width of 800 μm and a Channel Length of 100 μm in the Semiconductor Device Manufactured in Example 1 Was evaluated. The results of evaluating the mobility, subthreshold swing (SS) value, threshold voltage value required for switching transistors, and their variations when the drain voltage Vd is -0.2V and -2.0V are as follows. It is shown in Table 1.
[Table 1]

All the measured elements showed high mobility and high steep switching characteristics with extremely small threshold voltage, and their variations showed small values. From the above results, it was found that the device obtained by the present invention can produce high mobility and steep switching characteristics with low voltage and excellent yield.

According to the method described in a known document for manufacturing a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B (Japanese Patent Laid-Open No. 2014195794, Nature Cоmmun. 2016, 7, 11402-1-9). A semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B having a gate electrode, a source electrode, and a drain electrode formed by a printing process using silver nanoink was manufactured. First, a glass substrate was prepared as a substrate, and CYTOP CTL809M (registered trademark) manufactured by AGC Inc., which was a base film, was applied and formed on the substrate by a spin coating method. Next, after pattern irradiation with VUV light via a photomask, an ink containing silver nanoparticles described in the above-mentioned known document (Nature Cоmmun. 2016, 7, 11402-1-9) is coated with the blade coat described in the same known document. A film was formed by the method to prepare a gate electrode composed of silver nanoparticles. Next, CYTOP CTL809M was coated and formed by a spin coating method in the same manner as described above, and then pentafluorobenzenethiol was vapor-phase treated in the same manner as in Example 1 and silver was treated in the same manner as described above. Source electrodes, drain electrodes and guide electrodes made of nanoparticles were prepared. Next, the semiconductor layer is formed by forming the semiconductor material described in Example 1 by the same method as that described in Example 1, and forming an organic semiconductor device in which the semiconductor film is formed only at necessary locations. Manufactured. In order to more clearly observe the film-forming state of the semiconductor layer of the organic semiconductor device, a source and drain electrode layer composed of a CYTOP layer and silver nanoparticles was formed on a silicon substrate with an oxide film by the same method as described above. Cross Nicole observation using a polarization microscope of an organic semiconductor device in which an organic semiconductor layer is patterned on a substrate in the same manner as in the above method, that is, the semiconductor layer is formed under the same conditions as the semiconductor device. A photograph of the semiconductor device obtained in FIG. 22 is shown in FIG. When the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, the organic semiconductor film was formed on the CYTOP outside the region shown by the black dotted line in the figure. No blinking of the color indicating the above was observed, and it was confirmed that the organic semiconductor film was not formed. On the other hand, in the region surrounded by the conductive film shown by the dotted line, it was confirmed that the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.

Evaluation of Organic Semiconductor Device Described in Example 6 The organic thin film transistor characteristics of an organic thin film transistor element composed of a source electrode and a drain electrode having a channel width of 800 μm and a channel length of 200 μm included in the semiconductor device manufactured in Example 6 were measured. In this organic thin film transistor device, the capacitance of the CYTOP CTL809M layer, which plays the role of an insulating film, was calculated based on the experimentally obtained value, and the device characteristic value was calculated as ^{2.9 nF / cm 2.} Similar to the transistor element described in Example 1, the organic thin-film transistor element showed the shape of linear / saturated output / transmission characteristics typical of an organic field-effect transistor without hysteresis. When the carrier mobility of the organic thin film transistor element was calculated from the obtained characteristics, it showed a high mobility ^{of 2.0 cm 2 / Vs at the maximum under low voltage drive (drain voltage Vd = −0.5 V).} Further, when the sub-threshold swing (SS) value indicating that the drain current changes abruptly in the vicinity of the threshold voltage was calculated, the value was 170 mV / dec, showing an extremely steep switching characteristic.

In contrast to the method described in Example 1 of manufacturing a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B, manufacturing a gold electrode which is a conductive film is described in Example 7. Instead of manufacturing with silver nanoparticles using a printing process, the semiconductor solution used for manufacturing the semiconductor layer is No. 1 which is the following known organic semiconductor material. 3 and No. No. 4 was dissolved in chlorobenzene so that the mass concentration was 0.05%, and then No. 3: No. A conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B was prepared by the same method as that described in Example 1 except that the solution was changed to a mixed solution at a volume ratio of 4 = 9: 1. Manufactured semiconductor devices including.

FIG. 23 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope. When the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, the organic semiconductor film was formed on the CYTOP outside the region shown by the black dotted line in the figure. No blinking of the color indicating the above was observed, and it was confirmed that the organic semiconductor film was not formed. On the other hand, in the region surrounded by the conductive film shown by the dotted line, it was confirmed that the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.

Evaluation of Organic Semiconductor Device Described in Example 8 The organic thin film transistor characteristics of an organic thin film transistor element composed of a source electrode and a drain electrode having a channel width of 800 μm and a channel length of 80 μm included in the semiconductor device manufactured in Example 8 were measured. In this organic thin film transistor element, SiO _{2 as} a thermal oxide film layer and CYTOP CTL809M as an undercoat film play the role of an insulating film, and the element characteristic value was calculated ^{assuming that the capacitance is 2.5 nF / cm 2.} Similar to the transistor element described in Example 1, the organic thin-film transistor element showed the shape of linear / saturated output / transmission characteristics typical of an organic field-effect transistor without hysteresis. Total 15 performs measurement of element, where the resulting characteristics were calculated carrier mobility of the organic thin-film transistor element, in the low-voltage driving (the drain voltage Vd = -5V) mobility of average 0.29 cm 2 / ^Vs Indicated. Further, when the sub-threshold swing (SS) value indicating that the drain current changes abruptly in the vicinity of the threshold voltage was calculated, the value was 230 ± 40 mV / dec, and an extremely steep switching characteristic was shown with a small variation.

Manufacture of Semiconductor Device with Only Conductive 23 shown in FIGS. 3A and 3B A semiconductor having a U-shaped electrode pattern included in the semiconductor device device manufactured by the present invention is formed by forming a film by a blade coating method. We verified whether a thin film could be formed. CYTOP CTL809M, which is a base film, is applied to a silicon substrate with an oxide film by a spin coating method to form a film, and then VUV light is patterned and irradiated through a photomask, and then an ink containing silver nanoparticles is formed by a blade coating method. A conductive film made of silver nanoparticles was prepared. A semiconductor thin film was formed on this substrate by the same method as that described in Example 8. The obtained results are shown in FIG. In the figure, the semiconductor thin film was formed only in the region indicated by the black dotted line, and it was confirmed that the semiconductor could be patterned and formed by the arrangement of the conductive film according to the present invention.

For the method according to Example 1 of manufacturing a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B, the semiconductor solution used for forming the semiconductor layer is a known organic semiconductor material described below. No. A semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B was manufactured by the same method as that described in Example 1 except that the value was changed to 5.

FIG. 25 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope. When the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, the organic semiconductor film was formed on the CYTOP outside the region shown by the black dotted line in the figure. No blinking of the color indicating the above was observed, and it was confirmed that the organic semiconductor film was not formed. On the other hand, in the region surrounded by the conductive film shown by the dotted line, it was confirmed that the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.

Evaluation of Organic Semiconductor Device Described in Example 11 The organic thin film transistor characteristics of an organic thin film transistor element composed of a source electrode and a drain electrode having a channel width of 800 μm and a channel length of 100 μm included in the semiconductor device manufactured according to Example 11 were measured. In this organic thin film transistor element, SiO _{2 as} a thermal oxide film layer and CYTOP CTL809M as an undercoat film play the role of an insulating film, and the element characteristic value was calculated ^{assuming that the capacitance is 23 nF / cm 2.} Similar to the transistor element described in Example 1, the organic thin-film transistor element showed the shape of linear / saturated output / transmission characteristics typical of an organic field-effect transistor without hysteresis. When the carrier mobility of the organic thin film transistor element was calculated from the obtained characteristics, it showed a ^{maximum mobility of 4.4 cm 2 / Vs under low voltage drive (drain voltage Vd = −0.5 V).} Further, when the sub-threshold swing (SS) value indicating that the drain current changes abruptly in the vicinity of the threshold voltage was calculated, the value was 89 mV / dec at the minimum, showing an extremely steep switching characteristic.

In contrast to the method described in Example 1 of manufacturing a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B, a semiconductor solution used for producing a semiconductor layer is described in Example 11. No. which is an organic semiconductor material. 5 and the following known organic semiconductor material No. No. 6 was dissolved in chlorobenzene so that the mass concentration was 0.05%, and then No. 5: No. A conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B was prepared by the same method as that described in Example 1 except that the solution was changed to a mixed solution at a volume ratio of 6 = 8: 2. Manufactured semiconductor devices including.

FIG. 26 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope. The pattern of the conductive film in this example is the same as that shown in FIG. 16 used in Example 1, and the photograph shown in FIG. 25 shows a source electrode portion and a drain electrode portion that function as semiconductor devices. Is an enlargement of. When the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, the organic semiconductor film was formed on the CYTOP outside the region shown by the black dotted line in the figure. No blinking of the color indicating the above was observed, and it was confirmed that the organic semiconductor film was not formed. On the other hand, in the region surrounded by the conductive film shown by the dotted line, it was confirmed that the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.

Evaluation of Organic Semiconductor Device Described in Example 13 The organic thin film transistor characteristics of an organic thin film transistor element composed of a source electrode and a drain electrode having a channel width of 800 μm and a channel length of 200 μm included in the semiconductor device manufactured according to Example 13 were measured. In this organic thin film transistor element, SiO _{2 as} a thermal oxide film layer and CYTOP CTL809M as an undercoat film play the role of an insulating film, and the element characteristic value was calculated ^{assuming that the capacitance is 23 nF / cm 2.} Similar to the transistor element described in Example 1, the organic thin-film transistor element showed the shape of linear / saturated output / transmission characteristics typical of an organic field-effect transistor without hysteresis. When the carrier mobility of the organic thin film transistor element was calculated from the obtained characteristics, it showed a ^{maximum mobility of 0.79 cm 2 / Vs under low voltage drive (drain voltage Vd = −0.5 V).} Further, when the sub-threshold swing (SS) value indicating that the drain current changes abruptly in the vicinity of the threshold voltage was calculated, the value was 70 mV / dec, showing an extremely steep switching characteristic.

For the method according to Example 1 of manufacturing a semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B, a semiconductor solution used for forming a semiconductor layer is used as a commercially available organic semiconductor material. The method was the same as that described in Example 1 except that the semiconductor solution was blade-coated at a rate of 5.0 μm / sec by changing to a chlorobenzene solution of a certain poly (3-hexyl) thiophene (manufactured by Merck). A semiconductor device including a conductive film having a shape corresponding to the conductive film 23 shown in FIGS. 3A and 3B was manufactured. A photograph of the semiconductor device obtained by observation using a microscope is shown in FIG. 27. When a thin film is formed on the substrate, poly (3-hexyl) thiophene is observed in orange, so that the formed portion can be easily observed. In the figure, the organic semiconductor film is not formed on the CYTOP outside the region shown by the black dotted line, while the poly (3-hexyl) thiophene is formed in the region surrounded by the conductive film shown by the dotted line. It was confirmed that the film was formed without any defects.

For the process described in preparation example 1 of the semiconductor device including a conductive film having a corresponding shape to the conductive film 23 shown in FIGS. 3A and 3B, manufacturing of CYTOP silicon wafer with SiO ₂ thermal oxide film (100 nm) No film is formed, and instead, liquid repellent treatment by surface modification of the substrate is performed by exposing the vapor of 1H, 1H, 2H, 2H, -perfluorodecyltriethoxylan (FAS-17, manufactured by Merck) at 120 ° C. 3A and 3B have a shape corresponding to the conductive film 23 shown in FIGS. A semiconductor device including a conductive film was manufactured. FIG. 28 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope. When the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, it was found that the organic semiconductor film was formed on the CYTOP outside the region shown by the dotted line in the figure. No blinking of the indicated color was observed, and it was confirmed that the organic semiconductor film was not formed. On the other hand, in the region surrounded by the conductive film shown by the dotted line, it was confirmed that the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.

Manufacturing of a Semiconductor Device Containing a Conductive Included with a Conductive Conductor having a Shape Corresponding to the Conductive Conductor 23 shown in FIGS. , Au electrode was not exposed to PFBT steam, and the conductivity shown in FIGS. 3A and 3B was formed in the same manner as in Example 1 except that the semiconductor solution was blade-coated at a rate of 2.0 μm / sec. A semiconductor device including a conductive film having a shape corresponding to the film 23 was manufactured. FIG. 29 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope. When the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, it was found that the organic semiconductor film was formed on the CYTOP outside the region shown by the dotted line in the figure. No blinking of the indicated color was observed, and it was confirmed that the organic semiconductor film was not formed. On the other hand, in the region surrounded by the conductive film shown by the dotted line, it was confirmed that the highly crystalline organic semiconductor thin film having a plurality of crystal orientations was formed without defects.

Evaluation of wettability of the conductive film and the film underlying the semiconductor film The surface energy of the gold film subjected to the pentafluorobenzene thiol treatment, which is the conductive film used in Examples 1, 3, 11, 13, 15 and 16, was carried out. The surface energy of the insulating film layer of CYTOP CTL809M, which is the base of the semiconductor layer used in Examples 1, 3, 6, 7, 9, 11, 13, 15, and 17, and the surface treatment by FAS-17 used in Example 16 are performed. As an evaluation of the surface energy of the silicon substrate with a thermal oxide film and the surface energy of the gold film which is the conductive film used in Example 17, the contact angle when water and chlorobenzene droplets were dropped on the surface was measured. rice field. The results are shown in Table 2.
[Table 2]

The value of the contact angle of the organic solvents chlorobenzene and о-xylene used in the semiconductor solution in the examples is the insulation that is the substrate rather than the conductive film in all the combinations of the conductive film and the substrate of the semiconductor layer in the above examples. The film surface showed a larger value. In addition, the relationship between the water contact angles was the same as in the previous term.

Comparative Example 1

Manufacturing of a Semiconductor Device Containing a Conductive Material Not Included a Shape Corresponding to a Conductive Film 23 Shown in FIGS. 3A and 3B The shape corresponding to the conductive film 23 shown in FIGS. The semiconductor device was manufactured by the same method as that described in Example 1 except that the conductive film was formed so as to include only the

conductive films

19 and 21 shown in FIGS. 3A and 3B. FIG. 30 shows a photograph of the semiconductor device obtained by cross-nicol observation using a polarizing microscope. When the region where the crystalline organic semiconductor thin film was formed was determined from the blinking of the color by observing the cross Nicol, the organic semiconductor film was formed on the CYTOP outside the region shown by the dotted line on the right side of FIG. 29. No flickering of the color indicating was observed. On the other hand, the organic semiconductor thin film was formed only on the conductive film shown by the dotted line. Therefore, it is not possible to manufacture an organic semiconductor thin film in the channel region of a semiconductor device in which one of the conductive films is a source electrode and the other is a drain electrode, and a semiconductor device cannot be manufactured.

1,11: Substrate, 2,13: Underlayer film, 3,15: Conductive film, 150: Solution, 4,17: Insulating film, 5,6,19,21,23,23', 23''': Conductive Membrane, 6-1, 23-1, 23'-1, 23 "-1: 1st part, 6-2, 23-2, 23'-2, 23" -2: 2nd part, 6- 3, 23-3, 23'-3, 23''-3: 3rd part, 6-4, 23-4, 23'-4, 23''-4: 4th part, 6-5, 23- 5, 23'-5, 23''-5: 5th part, 23A-23C: Sub-conductive film, 23'''-6: One end, 23'''-7: Other end, 7, 25: Organic semiconductor film, 8-1 to 8-3, 30-1 to 30-3: region, 200, 300: blade, 250: solution

Claims

With the first conductive film
The insulating film on the first conductive film and
The second conductive film and the third conductive film on the insulating film,
The insulating film, the second conductive film, and the organic semiconductor film on the third conductive film are included.
The second conductive film includes a portion extending along the first direction.
The third conductive film is
The first portion located in the first direction when viewed from the second conductive film, and
Seen from the region between the second conductive film and the first portion, it is located in the second portion located in the second direction orthogonal to the first direction and in the third direction opposite to the second direction. Part 3 and
A fourth portion located in the fourth direction, which is the opposite direction of the first direction when viewed from the second portion,
Includes a fifth portion located in the fourth direction as viewed from the third portion.
The first part, at least a part of the second part, and at least a part of the third part are continuously extending.
A semiconductor device in which the surface free energy of the insulating film is smaller than the surface free energy of the second conductive film and the surface free energy of the third conductive film.
The third conductive film is
An upper portion extending along the first direction and the fourth direction and including the second portion and the fourth portion,
A lower portion extending along the first direction and the fourth direction and including the third portion and the fifth portion,
Extending along the second direction and the third direction, including an intermediate portion including the first portion.
The end on the first direction side of the upper portion and the end on the second direction side of the intermediate portion are continuous, and the end on the first direction side of the lower portion and the third direction side of the intermediate portion. The semiconductor device according to claim 1, wherein the ends of the semiconductor devices are continuous.
The third conductive film is
A part of the second part and an upper part including the fourth part extending along the first direction and the fourth direction, and
An upper portion extending along the first direction and the fourth direction, including a part of the third part and the fifth part, and
The upper portion is curved and extends from the end on the first direction side to the end on the first direction side of the lower portion, and the remaining portion of the first portion, the second portion, and the third portion is formed. The semiconductor device according to claim 1, further comprising a central portion including.
The first conductive film functions as a gate and serves as a gate.
The second conductive film functions as one of a source and a drain, and serves as one of a source and a drain.
The semiconductor device according to any one of claims 1 to 3, wherein the third electrode film functions as the other of a source and a drain.
The third conductive film includes a plurality of separated sub-conductive films.
The semiconductor device according to claim 1, wherein at least one of the first portion to the fifth portion includes at least a part of each of at least two sub conductive films among the plurality of sub conductive films.
The first conductive film functions as a gate and serves as a gate.
The second conductive film functions as one of a source and a drain, and serves as one of a source and a drain.
The semiconductor device according to claim 5, wherein at least one of the plurality of subconductive films functions as the other of the source and the drain.
The semiconductor device according to any one of claims 1 to 6, wherein the second conductive film and the third conductive film are made of the same material.
Further including a fourth conductive film on the insulating film, which includes a portion extending substantially parallel to the second conductive film, and the portion is located between the fourth portion and the fifth portion.
The first conductive film functions as a gate and serves as a gate.
The second conductive film functions as one of a source and a drain, and serves as one of a source and a drain.
The semiconductor device according to any one of claims 1 to 3 and 5, wherein the fourth conductive film functions as the other of a source and a drain.
The semiconductor device according to claim 8, wherein the second conductive film, the third conductive film, and the fourth conductive film are made of the same material.
The semiconductor device according to any one of claims 1 to 9, wherein the insulating film contains a fluororesin.
The semiconductor device according to any one of claims 1 to 9, wherein the insulating film contains a perfluoro (3 butenyl vinyl ether) polymer.
The semiconductor device according to any one of claims 1 to 11, wherein the organic semiconductor film includes a high molecular weight organic semiconductor material or a low molecular weight organic semiconductor material.
The semiconductor device according to claim 12, wherein the small molecule organic semiconductor material is a compound having an acene skeleton or a heteroacene skeleton.
The base film under the first conductive film and
The semiconductor device according to any one of claims 1 to 13, further comprising a substrate under the undercoat.
The semiconductor device according to claim 14, wherein the base film contains a fluororesin.
The semiconductor device according to claim 14, wherein the base film contains a perfluoro (3-butenyl vinyl ether) polymer.
The semiconductor device according to any one of claims 14 to 16, wherein the substrate is flexible.
The process of forming the first conductive film and
The step of forming an insulating film on the first conductive film and
The step of irradiating the first region and the second region of the insulating film with ultraviolet rays,
A step of forming a second conductive film and a third conductive film in the first region and the second region, respectively.
A step of forming an organic semiconductor film on the insulating film, the second conductive film, and the third conductive film is included.
The first region extends along the first direction and extends.
The second region is
The first portion located in the first direction when viewed from the first region, and
A second portion located in the second direction orthogonal to the first direction and a third direction located in the third direction opposite to the second direction when viewed from the region between the first region and the first portion. 3 parts and
A fourth portion located in the fourth direction, which is the opposite direction of the first direction when viewed from the second portion,
Includes a fifth portion located in the fourth direction as viewed from the third portion.
The first part, at least a part of the second part, and at least a part of the third part are continuously extending.
The contact angle of the solvent, which is the main component of the solution containing the material constituting the organic semiconductor film as a solute, with respect to the gate insulating film is larger than the contact angle of the solvent with respect to each of the second conductive film and the third conductive film. big,
A method for manufacturing a semiconductor device, wherein the step of forming the organic semiconductor film includes a step of applying the solution along the fourth direction.
The process of forming the first conductive film and
The step of forming an insulating film on the first conductive film and
A step of irradiating the first region, the second region, and the third region of the insulating film with ultraviolet rays, and
A step of forming a second conductive film, a third conductive film, and a fourth conductive film in the first region, the second region, and the third region, respectively.
A step of forming an organic semiconductor film on the insulating film, the second conductive film, the third conductive film, and the fourth conductive film is included.
The first region and the third region extend substantially in parallel along the first direction.
The second region is
The first portion located in the first direction when viewed from the first region and the third region, and
The second portion located in the second direction orthogonal to the first direction and the third direction opposite to the second direction when viewed from the first region and the region between the third region and the first portion. The third part located in the direction and
A fourth portion located in the fourth direction, which is the opposite direction of the first direction when viewed from the second portion,
Includes a fifth portion located in the fourth direction as viewed from the third portion.
The first part, at least a part of the second part, and at least a part of the third part are continuously extending.
The contact angle of the solvent, which is the main component of the solution containing the material constituting the organic semiconductor film as a solute, with respect to the gate insulating film is the contact angle of the solvent with respect to the second conductive film, the third conductive film and the fourth conductive film. Greater than the contact angle for each
A method for manufacturing a semiconductor device, wherein the step of forming the organic semiconductor film includes a step of applying the solution along the fourth direction.
The coating step is
The step of dropping the solution onto the insulating film and
The method for manufacturing a semiconductor device according to claim 18 or 19, further comprising a step of sweeping the solution along the fourth direction by a coating member.
The method for manufacturing a semiconductor device according to claim 20, further comprising a step of liquid-repellent processing the surface of the coating member so as to have liquid-repellent property against the solvent before the step of forming the organic semiconductor film.