Method for manufacturing a patterned organic film, apparatus for manufacturing a patterned organic film, organic semiconductor device produced thereby, and integrated circuit including the organic semiconductor device

Abstract

The present disclosure provides a patterning method that enables patterning of an organic semiconductor film without damaging same, that does not damage an underlying substrate, insulating film, or the like, that is applicable to a wide variety of organic materials, particularly organic semiconductor materials, and that is capable of performing patterning at low cost. The present disclosure pertains to a method that is for producing a patterned organic film and that comprises: forming a hydrophobic organic film on a first substrate that is hydrophilic and water-insoluble, by using a coating method; pressing the organic film formed on the first substrate against protrusions of a stamp having the protrusions and recesses; transferring the organic film to the protrusions by applying water or an aqueous solution to an interface between the first substrate and the organic film; and pressing the organic film transferred to the protrusions against a second substrate to transfer the organic film to the second substrate, and thereby obtaining a patterned organic film. At least the organic film or the second substrate is an organic semiconductor.

Description

Technical Field

[0001] The present disclosure relates to a method and apparatus for manufacturing a patterned organic film, and an organic semiconductor device and an integrated circuit including the organic semiconductor device manufactured thereby.

Background Art

[0002] In recent years, interest in organic semiconductors has been increasing. Characteristics of organic semiconductors include excellent flexibility and the ability to be inexpensively formed into large areas by a roll to roll process, which are different from conventional inorganic semiconductors such as amorphous silicon and polycrystalline silicon. Therefore, organic semiconductors are being considered for application to next-generation electronic devices as post-silicon semiconductors.

[0003] In addition, organic semiconductors can be used to fabricate devices by a low-cost solution process and are attracting attention as basic elements of next-generation electronic devices important in the Internet of Things (IoT) society. In circuit applications for industrialization, particularly in logic circuit applications of organic field effect transistors, patterning of an organic semiconductor film (hereinafter also referred to as a semiconductor film) is essential.

[0004] Typical examples of semiconductor film patterning methods reported so far include a method of forming a semiconductor film only in necessary locations, or a method of forming a film over the entire surface and then etching using a photolithography process or the like.

[0005] Examples of semiconductor film patterning methods include laser etching, photolithography (dry etching using plasma), and photolithography (wet etching).

[0006] In addition, Nanotransfer printing (nTP) has been proposed as a patterning method for fine electrodes and the like (Non-Patent Document 1).

Prior Art Documents

Non-Patent Documents

[0007]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] Laser etching for etching a semiconductor film with a laser is costly and likely to damage an underlying insulating film or the like by the laser.

[0009] Photolithography that performs dry etching using plasma can obtain high resolution and high reliability, but it is costly and may damage the substrate, such as etching the substrate by the plasma.

[0010] Photolithography that performs wet etching using a solvent can obtain high resolution and relatively high reliability, but it is costly, the substrate may swell, and the portion that is desired to remain after photolithography may flow away. Also, it is difficult to select an appropriate solvent according to the semiconductor material.

[0011] In nTP, Au / Ti (Ti on top) is deposited on the entire surface of a stamp with unevenness, and both the glass substrate to be transferred and Au / Ti are subjected to plasma treatment or the like to form hydroxyl groups on the surface, and they are brought into close contact in a state where hydroxyl groups are formed. The hydroxyl groups chemically bond to each other, and the Au / Ti pattern on the convex portion of the stamp is transferred onto the glass substrate.

[0012] In nTP, as long as a mold is fabricated, expensive photolithography equipment and resist are not required. However, since it utilizes the condensation reaction between hydroxyl groups, it is limited to materials on which hydroxyl groups are formed on the surface, has no versatility, and cannot be used for the transfer of organic semiconductors.

[0013] When forming a film only at necessary locations, there is a problem that it is difficult to control the crystal growth direction, which is important for obtaining high-performance electrical characteristics.

[0014] When etching after forming a film over the entire surface, although it is possible to fabricate a circuit using a high-performance semiconductor film, since plasma or an organic solvent is used as the etching method, there is a concern about damage to the underlying layer below the semiconductor film, and it is necessary to select an organic solvent for each organic semiconductor material.

[0015] In view of these, as a patterning method, it is required that patterning can be performed without damaging the organic semiconductor film, that the underlying substrate, insulating film, etc. are not damaged, that it is applicable to a wide variety of organic materials, particularly organic semiconductor materials, and that it is low-cost.

Means for Solving the Problem

[0016] The inventor has found a method of patterning by transferring an organic film on a film onto the convex portions of a stamp having concavo-convex patterns and then pressing the stamp onto a target substrate, whereby only the organic film on the convex portions is transferred onto the target substrate.

[0017] The gist of the present invention is as follows. (1) Using a coating method, forming a hydrophobic organic film on a hydrophilic and water-insoluble first substrate, Pressing the organic film formed on the first substrate against the convex portions of a stamp having convex and concave portions, Applying water or an aqueous solution to the interface between the first substrate and the organic film to transfer the organic film to the convex portions, and Pressing the organic film transferred to the convex portions against a second substrate to transfer the organic film to the second substrate and obtain a patterned organic film, including, at least one of the organic film and the second substrate is an organic semiconductor, A method for manufacturing a patterned organic film. (2) The manufacturing method according to (1) above, wherein the distance between the uppermost part of the convex portion and the lowermost part of the concave portion is 2 to 100 μm. (3) The manufacturing method according to (1) or (2) above, wherein the patterned organic film includes 10 or more organic films, each organic film having a thickness of 2 nm or more, a width of 500 nm or more, and a length of 500 nm or more, and the distance between adjacent organic films is 1 μm or more. (4) A stamp placement unit configured to place a stamp having convex and concave portions. A first substrate placement unit configured to be able to place a hydrophilic and water-insoluble first substrate having an organic film on its surface. A second substrate placement unit configured to be able to place a second substrate. A first drive unit configured to be able to move at least one of the first substrate and the stamp so as to press the organic film on the first substrate against the convex portion of the stamp to place the organic film on the convex portion and to separate the first substrate from the organic film placed on the convex portion. A first control unit configured to control the force for pressing the organic film on the first substrate against the convex portion of the stamp. A water or aqueous solution supply unit configured to supply water or an aqueous solution to the interface between the organic film and the first substrate. A second drive unit configured to be able to move at least one of the stamp and the second substrate so as to press the organic film placed on the convex portion of the stamp against the second substrate to place the patterned organic film on the second substrate and to separate the stamp from the patterned organic film placed on the second substrate, and A second control unit configured to control the force for pressing the organic film placed on the convex portion of the stamp against the second substrate. A manufacturing apparatus for a patterned organic film, including the above. (5) The manufacturing apparatus according to (4) above, wherein the first control unit is configured to control the distribution of the pressing force in the plane of the organic film when pressing the organic film against the convex portion. (6) The manufacturing apparatus according to (4) or (5) above, wherein the second control unit is configured to control the distribution of the pressing force in the plane of the organic film when pressing the organic film against the second substrate. (7) The manufacturing apparatus according to any one of (4) to (6) above, wherein the manufacturing apparatus includes an amount adjustment unit for water or an aqueous solution that is configured to be able to adjust the amount of water or the aqueous solution supplied by the water or aqueous solution supply unit. (8) The manufacturing apparatus according to any one of (4) to (7) above, wherein the manufacturing apparatus includes a supply position adjustment unit that recognizes the position of the interface for supplying the water or aqueous solution and is capable of adjusting the position of the water or aqueous solution supplied by the water or aqueous solution supply unit. (9) The manufacturing apparatus according to any one of (4) to (8) above, wherein the manufacturing apparatus includes a first alignment unit that controls the position where the organic film is pressed against the convex portion. (10) The manufacturing apparatus according to any one of (4) to (9) above, wherein the manufacturing apparatus includes a second alignment unit that controls the position where the organic film on the convex portion of the stamp is pressed against the second substrate. (11) A substrate, and a patterned organic film on the substrate is included, the organic film is hydrophobic, at least one of the organic film and the substrate is an organic semiconductor, the substrate has no damage caused by the patterning of the organic film, an organic semiconductor device. (12) The organic semiconductor device according to (11) above, wherein the patterned organic film includes 10 or more organic films, each organic film having a thickness of 2 nm or more, a width of 500 nm or more, and a length of 500 nm or more, and the distance between adjacent organic films is 1 μm or more. (13) The organic semiconductor device according to (11) or (12) above, wherein the patterned organic film is an organic semiconductor single crystal film having a single domain of 0.0001 mm 2 or more. (14) The organic semiconductor device according to any one of (11) to (13) above, including electrodes in at least a part between the substrate and the organic film, at least a part on the side opposite to the substrate with respect to the organic film, or both of them. (15) The organic semiconductor device according to (14) above, including a space between the substrate, the organic film, and the electrode. (16) An integrated circuit including the organic semiconductor device according to any one of claims 11 to 15.

Advantages of the Invention

[0018] According to the method of the present disclosure, patterning of the organic film can be performed at low cost without damaging the organic film and its underlying layer by an organic solvent, plasma, or the like. Further, since the method of the present disclosure is a physical patterning technique using unevenness, it is applicable to a wide variety of organic materials, particularly organic semiconductor materials.

Brief Description of the Drawings

[0019]

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Mode for Carrying Out the Invention

[0020] The present disclosure relates to a method for manufacturing a patterned organic film, which includes forming a hydrophobic organic film on a hydrophilic and water-insoluble first substrate using a coating method, pressing the organic film formed on the first substrate against the convex portions of a stamp having convex and concave portions, applying water or an aqueous solution to the interface between the first substrate and the organic film to transfer the organic film to the convex portions, and pressing the organic film transferred to the convex portions against a second substrate to transfer the organic film to the second substrate to obtain a patterned organic film, wherein at least one of the organic film and the second substrate is an organic semiconductor.

[0021] The manufacturing method of the present disclosure mainly has the following remarkable effects. If a mold is prepared, photolithography is not required and the cost is low. Since patterning of the organic film can be performed simultaneously with transfer to the stamp, patterning can be performed in a short time. Since patterning of the organic film is physically performed using the unevenness of the stamp, there is no need to use a solvent or a laser, and patterning of various organic materials can be performed, and the versatility is high. Since only the stamp needs to be pressed against the second substrate, the second substrate is not damaged by a solvent or the like. For example, even when the second substrate is soluble in a solvent that dissolves the organic material, a patterned organic film can be formed. The stamp only comes into contact with water or an aqueous solution and does not need to be contacted with a solvent or heated, so there is substantially no swelling or shrinkage of the stamp due to the solvent or heat. For example, a film that has been previously coated and has become a single crystal can be patterned. Different from nTP, it does not require bonding by a hydroxyl group with the transfer destination substrate.

[0022] Also, conventionally, when forming a semiconductor film by photolithography, a mask is required on the material to be etched, and a patterned electrode is often used as the mask for photolithography. However, when the patterned electrode is disposed below the semiconductor film, the electrode cannot be used as a mask, and it is necessary to separately prepare a mask that does not damage the semiconductor film. According to the method of the present disclosure, even when the patterned electrode is disposed below the semiconductor film, a patterned semiconductor film can be obtained on the electrode without requiring an additional process.

[0023] Also, compared with the conventional method of forming a semiconductor film only on necessary portions, according to the manufacturing method of the present disclosure, since it is possible to use a single-crystalline domain with aligned crystal growth directions, high carrier conduction characteristics can be expected. Furthermore, compared with the case of using a photolithography process or the like, the manufacturing method of the present disclosure can be expected to have the effects of low cost and short working time.

[0024] The manufacturing method of the present disclosure is applicable to many semiconductor materials and underlying layers while maintaining high-performance electrical characteristics of organic films such as organic semiconductor single crystals and organic semiconductor polymers, and has high utility value in the mass production process in the printed electronics industry.

[0025] In the manufacturing method of the present disclosure, a water-resistant organic film is formed on a hydrophilic and water-insoluble first substrate by a coating method. The coating method is a method of preparing an organic solution by dissolving an organic material in an organic solvent, applying the organic solution on a substrate, and evaporating the organic solvent to form a film. As the organic solvent, an organic solvent conventionally used in the coating method can be used, for example, toluene, dichlorobenzene, or the like can be used.

[0026] As the coating method, a conventionally used method can be employed. For example, an edge casting method, a continuous edge casting method, a drop casting method, a spin coating method, a printing method (inkjet method or gravure printing method), a dispenser method, a spray method, a dip coating method, a die coater method, a roll coater method, a bar coater method, a blade coating method, etc. can be used.

[0027] The first substrate is a hydrophilic substrate with a water contact angle preferably of 20 degrees or less, more preferably 10 degrees or less. The first substrate can be a substrate with a hydrophilic surface or a substrate whose surface has been hydrophilized. A glass substrate or mica is preferred, and more preferably a glass substrate. The glass substrate is preferably Eagle glass. The hydrophilization treatment can be carried out by subjecting the glass substrate to a UV / O 3 treatment.

[0028] The first substrate is water-insoluble and can be, for example, mica or glass. Since the first substrate is water-insoluble, when water or an aqueous solution is applied to the interface between the first substrate and the organic film, the components of the first substrate do not elute and adhere to or react with the organic film, and a high-purity organic film can be obtained. Also, when water or an aqueous solution is applied to the interface between the first substrate and the organic film, the shape of the first substrate is maintained without collapsing, so that the organic film can be separated from the first substrate without distorting the shape of the organic film. Water-insoluble means not substantially dissolving, decomposing, or swelling in water or an aqueous solution. The glass is preferably one hydrophilized by UV-ozone treatment or a hydrophilic coating material, etc. on the surface. The first substrate may have flexibility.

[0029] In the manufacturing method of the present disclosure, water or an aqueous solution is applied to the interface between the first substrate and the organic film to separate the organic film from the first substrate. The organic film can be a desired organic film as long as it is a hydrophobic organic film. Water or an aqueous solution enters between the hydrophilic first substrate and the molecules of the hydrophobic organic film, and the organic film can be separated from the first substrate.

[0030] To separate the organic film from the first substrate, water or an aqueous solution is used, preferably an aqueous solution. The aqueous solution penetrates more easily than water at the interface between the first substrate and the organic film, and the separation of the organic film from the first substrate is further promoted. The aqueous solution can be one that is difficult to swell or shrink the stamp, and is a mixture of water and preferably a polar solvent such as ethanol, methanol, or acetonitrile. The concentration of the polar solvent such as ethanol, methanol, or acetonitrile in the aqueous solution is preferably 5 to 50%, more preferably 10 to 45%, still more preferably 15 to 40%.

[0031] The water contact angle of the hydrophilic first substrate is smaller than that of the hydrophobic organic film, and the difference in the water contact angle between the first substrate and the organic film is preferably 40 degrees or more, more preferably 50 degrees or more, still more preferably 60 degrees or more, even more preferably 70 degrees or more, even more preferably 80 degrees or more, even more preferably 90 degrees or more. The contact angle of the organic film is preferably 60 degrees or more, more preferably 70 degrees or more, still more preferably 80 degrees or more, even more preferably 100 to 120 degrees. When the difference in the contact angle between the hydrophilic first substrate and the hydrophobic organic film is within the preferred range, the organic film can be peeled off from the first substrate more stably.

[0032] The method of applying water or an aqueous solution to the interface between the first substrate and the organic film is not particularly limited, and methods such as dropping water or an aqueous solution using a water supply device such as a dropper at the interface between the first substrate and the organic film, and immersing the first substrate on which the organic film is formed in water can be used.

[0033] In this specification, hydrophobicity can preferably have a contact angle of 50 degrees or more, more preferably 60 degrees or more, still more preferably 70 degrees or more, even more preferably 80 degrees or more, more preferably 90 degrees or more, still more preferably 100 degrees or more, even more preferably 110 degrees or more, even more preferably 150 degrees or more.

[0034] The area of the organic film formed on the first substrate is preferably 2 mm 2 or more, more preferably 10 mm 2 or more, still more preferably 100 mm 2 or more, even more preferably 1000 mm 2 or more, even more preferably 10000 mm 2 or more. The upper limit of the area of the organic film is not particularly limited and is limited by the size of the manufacturing equipment, and may be, for example, 10 m 2 for example. When used in a semiconductor device, the organic film having the above preferred area is, for example, less than 0.000025 to 2.0 mm 2 less than 0.0001 to 1.5 mm 2 less than 0.0004 to 1.0 mm 2 0.0009 mm 2 to 0.5 mm 2 0.0016 to 0.2 mm 2 0.0025 to 0.1 mm 2 or 0.005 mm to 0.05 mm 2 and may be used separately after being separated into areas of.

[0035] The distance between the uppermost part of the convex portion of the stamp and the lowermost part of the concave portion is preferably 2 to 100 μm, more preferably 5 to 50 μm, still more preferably 7 to 40 μm, and even more preferably 10 to 30 μm. When the distance between the uppermost part of the convex portion of the stamp and the lowermost part of the concave portion is within the above preferred range, physical patterning can be performed while suppressing the contact of the concave portion with the organic film and suppressing the breakage of the convex portion when the stamp and the organic film are pressed against each other.

[0036] The pressure per unit area of the convex portion when pressing the organic film against the convex portion of the stamp may be appropriately adjusted within a range where the concave portion does not contact the organic film and the convex portion does not break, and can be, for example, 5 to 200 kPa, 10 to 100 kPa, or 50 to 80 kPa.

[0037] When pressing the organic film transferred to the convex portion of the stamp against the second substrate, the pressure per unit area of the convex portion may be appropriately adjusted within the range where the organic film is transferred to the second substrate and the convex portion does not break. For example, it can be 5 to 200 kPa, 10 to 100 kPa, or 50 to 80 kPa.

[0038] The constituent material of the stamp is preferably a resin, preferably polydimethylsiloxane (PDMS) or polymethyl methacrylate (PMMA), and more preferably PDMS. The constituent material of the stamp may have PDMS or PMMA as a main constituent element. By using a stamp composed of such a material, the transfer of the organic film to the convex portion of the stamp and the transfer of the organic film from the convex portion of the stamp to the second substrate can be performed well. The stamp may be hydrophobic. The stamp may be provided with a support substrate of glass or film.

[0039] The support substrate is preferably a glass substrate, a polyethylene naphthalate (PEN) substrate, or a polyethylene terephthalate (PET) substrate.

[0040] The glass substrate, PEN substrate, or PET substrate (depending on the heat treatment temperature during stamp production) can be selected based on the ease of pressing the stamp material before curing and the ease of peeling from the stamp production mold after heat curing. Using a flexible substrate as the base material of the stamp facilitates peeling.

[0041] A release layer may be formed on the surface of the stamp. The release layer is preferably CYTOP or a self-assembled monolayer (SAM), more preferably CYTOP. The self-assembled monolayer is, for example, decyltrimethoxysilane (DTS), triethoxy-1H,1H,2H,2H-heptadecafluorodecylsilane (F-SAM), or trimethoxy(2-phenylethyl)silane (β-PTS). Since DTS has a contact angle of about 101 degrees, F-SAM has a contact angle of about 110 degrees, and β-PTS has a contact angle of about 80 degrees, when transferring the organic film to the second substrate, the organic film can be more easily peeled off from the stamp and is easier to transfer. The SAM treatment can be performed by a vapor phase method or a liquid phase method.

[0042] The patterned organic film preferably includes 10 or more organic films, each organic film having a thickness of 2 nm or more, a width of 500 nm or more, and a length of 500 nm or more, and the distance between adjacent organic films is 1 μm or more.

[0043] The number of organic films included in the patterned organic film is more preferably 50 or more, and even more preferably 100 or more. The width and length of the organic film are each more preferably 10 μm or more, even more preferably 15 μm or more, even more preferably 20 μm or more, even more preferably 30 μm or more, even more preferably 45 μm or more, and even more preferably 50 μm or more. The thickness of the organic film is more preferably 2 to 100 nm, and even more preferably 7 to 20 nm. The distance between adjacent organic films is more preferably 5 μm or more, even more preferably 10 μm or more, even more preferably 20 μm or more, and even more preferably 25 μm or more.

[0044] The upper limit of the width of the organic film is not particularly limited, for example, it is 500 μm or less. The upper limit of the distance between the organic films in the organic film is not particularly limited.

[0045] Figure 22 shows a top view photograph of an example of a patterned organic film, which is a set of five organic films. Figure 23 shows a top view photograph of another example of a patterned organic film, which is a set of five organic films. Figure 33 shows an external photograph of a 4-inch silicon wafer having a patterned semiconductor organic film.

[0046] At least a part of the surface of the second substrate in contact with the patterned organic film may have properties such as hydrophobicity, solvent solubility, non-heat resistance, or a combination thereof. Preferably, the entire surface of the second substrate in contact with the organic film has properties such as hydrophobicity, solvent solubility, non-heat resistance, or a combination thereof. More preferably, the entire second substrate has properties such as hydrophobicity, solvent solubility, non-heat resistance, or a combination thereof.

[0047] The material of the second substrate is not particularly limited as long as it is solid. The second substrate may include a plurality of layers such as a support substrate, an electrode, and an insulating film. The second substrate may be a flexible substrate. Examples of the flexible substrate include a polyethylene naphthalate (PEN) substrate, a polyimide substrate, a polyphenylene sulfide substrate, and a silicone substrate.

[0048] At least a part of the surface of the second substrate in contact with the organic film, preferably the entire surface of the second substrate in contact with the organic film, more preferably the entire second substrate may exhibit hydrophobicity within the preferred range. By the second substrate exhibiting such hydrophobicity, when manufacturing a device using a patterned organic film disposed on a hydrophobic substrate, moisture (adsorbed molecules) that can adhere to the substrate can be reduced or eliminated, and a device having good characteristics without the influence of moisture can be manufactured.

[0049] Examples of materials exhibiting hydrophobicity include, for example, parylene (contact angle of about 80 to 90 degrees), CYTOP (registered trademark) of a fluoropolymer (contact angle of 110 degrees), and the like.

[0050] At least a part of the surface of the second substrate in contact with the organic film, preferably the entire surface of the second substrate in contact with the organic film, more preferably the entire second substrate, may be soluble in a solvent. Therefore, at least a part of the surface of the second substrate in contact with the organic film, preferably the entire surface of the second substrate in contact with the organic film, more preferably the entire second substrate, may be a p-type organic semiconductor film or an n-type organic semiconductor film, or may be a laminate including a p-type organic semiconductor film and an n-type organic semiconductor film. Accordingly, the second substrate can include a pn junction structure, a pnp junction structure, or an npn junction structure formed by the organic semiconductor film.

[0051] In the present application, "soluble in a solvent" means being substantially dissolved, decomposed, or swollen in an organic solvent, for example, being substantially dissolved, decomposed, or swollen in an organic solvent conventionally used in a coating method such as toluene or dichlorobenzene.

[0052] At least a part of the surface of the second substrate in contact with the organic film, preferably the entire surface of the second substrate in contact with the organic film, more preferably the entire second substrate, may be non-heat-resistant. Therefore, at least a part of the surface of the second substrate in contact with the organic film, preferably the entire surface of the second substrate in contact with the organic film, more preferably the entire second substrate, may be a substrate having an electrode film such as Au modified with a self-assembled monolayer (SAM) such as pentafluorobenzenethiol (PFBT). An organic film can be disposed on such a modification material with low heat resistance such as PFBT.

[0053] In the present application, "non-heat-resistant" preferably means having a glass transition point of 90°C or lower, or sublimating, melting, or decomposing at 90°C or lower, and more preferably means having a glass transition point of 120°C or lower, or sublimating, melting, or decomposing at 120°C or lower.

[0054] The manufacturing method of the present disclosure will be described with reference to the drawings.

[0055] Using a coating method, a hydrophobic organic film is coated on a hydrophilic and water-insoluble first substrate. Next, as shown in FIG. 1, the organic film 20 on the first substrate 10 is pressed against the convex portion 31 of the stamp 30. The stamp 30 has a convex portion 31 and a concave portion 32.

[0056] As shown in FIG. 2, while bringing the organic film 20 on the first substrate 10 into close contact with the convex portion of the stamp 30, water or an aqueous solution is applied to the interface between the first substrate 10 and the organic film 20. FIG. 2 shows a mode in which water or an aqueous solution is applied to the interface between the first substrate 10 and the organic film 20 using a supplier 80 of water or an aqueous solution such as a dropper.

[0057] Thereby, water or an aqueous solution penetrates between the hydrophilic glass substrate and the highly water-repellent organic film, the organic film peels off from the substrate, and the organic film 21 is transferred onto the convex portion of the stamp 30 as shown in FIG. 3. When transferring the organic film onto the convex portion of the stamp, the organic film 22 may be transferred to the concave portion as illustrated in FIG. 3.

[0058] Next, as shown in FIG. 4, the organic film 21 transferred to the convex portion is pressed against the second substrate 40, and as shown in FIG. 5, the organic film 21 is transferred to the second substrate 40 to obtain a patterned organic film. The second substrate 40 may have a hydrophobic film 42.

[0059] (Mold production) In the manufacturing method of the present disclosure, the stamp used can be manufactured using a mold. The mold for manufacturing the stamp can be manufactured by a conventional method. An example of the method for manufacturing the mold is shown below.

[0060] Prepare a substrate. The substrate can be a substrate whose surface has been hydrophilized, and a glass substrate is preferred. By having a hydrophilic surface, the adhesion of the photoresist can be improved. The glass substrate is preferably Eagle glass. The hydrophilization treatment can be performed by subjecting the glass substrate to UV / O 3 treatment or plasma treatment.

[0061] As shown in FIG. 6, after spin-coating a photoresist solution on a hydrophilic glass substrate 52, heat treatment is performed, followed by masking with a mask of a predetermined pattern and exposure. The photoresist is preferably SU-8. SU-8 can form a photoresist with a height of 10 μm or more and a pitch of 1 μm or less or 100 nm or less.

[0062] After exposure, heat treatment is performed at a low temperature, development is carried out, and heat treatment is performed at a high temperature. Subsequently, an F-SAM treatment or the like by a vapor phase method may be performed to form a release layer, and a mold 50 of a glass substrate 52 on which a photoresist 54 provided with a release layer 56 is formed can be produced.

[0063] (Stamp production) The stamp used in the manufacturing method of the present disclosure can be produced as follows using the produced mold 50. An example of a method for producing a stamp is shown below.

[0064] As shown in FIG. 7, a liquid stamp material 33 is dropped onto the mold 50, a weight 58 is placed thereon while being sandwiched by a support substrate 57, left standing, and then thermally cured. After that, the mold is peeled off to produce a stamp 30 as shown in FIG. 8. The stamp material may be stirred and defoamed before being dropped onto the mold.

[0065] In order to improve the peelability of the organic film, as shown in FIG. 8, a release layer 34 such as CYTOP may be formed on the surface of the produced stamp. The formation of the release layer is performed by spin-coating a solution containing the material of the release layer and then performing heat treatment.

[0066] The organic film can be, for example, an organic film such as PMMA, an organic semiconductor film, an organic semiconductor single crystal film, or an organic semiconductor polymer film. The organic film is preferably an organic semiconductor film, more preferably an organic semiconductor single crystal film or an organic semiconductor polymer film, and even more preferably an organic semiconductor single crystal film. The organic semiconductor includes a p-type organic semiconductor, an n-type organic semiconductor, or a combination thereof.

[0067] When the organic film is an organic semiconductor single crystal film, the average film thickness of the organic semiconductor single crystal film is 2 to 100 nm, preferably 4 to 20 nm. By the average film thickness of the organic semiconductor single crystal film being within the above range, good device characteristics can be obtained. The measurement of the average film thickness of the organic semiconductor single crystal film can be performed using a stylus surface profiler or an atomic force microscope.

[0068] The organic semiconductor single crystal film preferably has 1 to 50 molecular layers, more preferably 1 to 10 molecular layers, and still more preferably 1 to 5 molecular layers in the thickness direction. It is most preferable for the organic semiconductor single crystal film to have 1 molecular layer, but it may have 2 or more molecular layers in the thickness direction. The number of molecular layers of the organic semiconductor single crystal film can be measured with an atomic force microscope.

[0069] The thickness of one molecular layer of the organic semiconductor single crystal film is preferably 2 to 6 nm, more preferably 2 to 4 nm. The thickness of one molecular layer of the organic semiconductor single crystal film can be measured by combining single crystal X-ray structure analysis and atomic force microscope observation.

[0070] The organic semiconductor single crystal film consists of a single domain or multiple domains, and preferably consists of a single domain. The domain of the organic semiconductor single crystal film can be measured by single crystal X-ray diffraction. The organic semiconductor single crystal film is preferably 0.0001 mm 2 or more, more preferably 0.0004 mm 2 or more, still more preferably 0.0009 mm 2 or more, still more preferably 0.0016 mm 2 or more, still more preferably 0.0025 mm 2 or more, still more preferably 0.005 mm 2 or more, still more preferably 0.5 mm 2 or more, still more preferably 2.0 mm 2 or more, still more preferably 4.0 mm 2 or more, still more preferably 100 mm 2 or more, still more preferably 1000 mm 2More preferably, it is 10000 mm or more 2 It has a single domain with a continuous area of 2 or more. Whether the organic semiconductor single crystal film having the preferred area has a single domain can be confirmed by in-plane X-ray diffraction measurement in which X-rays are irradiated onto the entire organic semiconductor single crystal film having the preferred area. The area of the organic semiconductor single crystal layer may be the same as the area of the single domain. A single domain is a continuous region with aligned crystal orientations. It is preferable that the number of molecular layers is aligned in the single domain, but even if regions of different molecular layers are included as long as the crystal orientations are aligned. For example, when a region of three molecular layers in which a layer with aligned crystal orientations has grown dendritically is included on a part of a region of two molecular layers with aligned crystal orientations, the continuous region of the two molecular layers and the three molecular layers becomes a single domain.

[0071] It should be understood that, of course, the organic semiconductor single crystal film may incorporate separated organic semiconductor single crystal films having the single domain with the preferred continuous area. For example, the organic semiconductor single crystal film having the single domain with the preferred continuous area may be separated into a plurality of pieces of organic semiconductor single crystal films and incorporated into an organic semiconductor device. By separating each organic semiconductor single crystal film within the organic semiconductor device, it can be electrically isolated from other elements. That each separated organic semiconductor single crystal film is obtained from a single crystal film with aligned crystal axis directions can be confirmed by measurement using single crystal X-ray diffraction, electron beam diffraction, or observation with a polarization microscope.

[0072] Fig. 34 shows a laser confocal microscope image of an array in which 8×8 organic semiconductor single crystal films of 700 μm × 500 μm, which are transferred and patterned by the present method, are arranged. The portion surrounded by the square frame is one 700 μm × 500 μm organic semiconductor single crystal film, and the organic semiconductor single crystal films are aligned 8×8 in the whole microscope image. The interval between the organic semiconductor single crystal films is 500 μm in the horizontal direction and 300 μm in the vertical direction. The in-plane X-ray diffraction measurement can be carried out, for example, by irradiating X-rays to the portion surrounded by the broken line while rotating the substrate holding the organic semiconductor single crystal film shown in Fig. 34 by 360 degrees. As shown as an example in Fig. 35, if peaks are observed at 180-degree intervals by the in-plane X-ray diffraction measurement, it is determined that each organic semiconductor single crystal film located in the portion surrounded by the broken line irradiated with X-rays is a single crystal film substantially facing the same direction. When there is a significant variation in the crystal orientation, the diffraction peaks do not become one, and a plurality of peaks are observed. When the organic single crystal film transferred and patterned by the present method is measured by the above method, the full width at half maximum of the diffraction peak is preferably within ±1 degree, more preferably within ±0.5 degree.

[0073] The organic semiconductor single crystal film preferably has a mobility of 0.1 cm 2 / V·s or more, more preferably 0.5 cm 2 / V·s or more, still more preferably 1.0 cm 2 / V·s or more, even more preferably 3.0 cm 2 / V·s or more, even more preferably 2.0 cm 2 / V·s or more, even more preferably 5.0 cm 2 / V·s or more, even more preferably 7.5 cm 2 / V·s or more, even more preferably 10 cm 2 / V·s or more. The mobility of the organic semiconductor single crystal film can be calculated from the measurement results of the organic field effect transistor.

[0074] There is no particular limitation on the type of organic semiconductor constituting the organic semiconductor single crystal film. For example, polycyclic aromatic compounds having four or more rings, or polycyclic compounds having four or more rings composed of one or more unsaturated five-membered heterocyclic compounds and a plurality of benzene rings can be used.

[0075] In addition, the organic semiconductor constituting the organic semiconductor single crystal film is preferably a material having a high self-condensation function. For example, p-type organic semiconductors such as Cn-DNBDT-NW of the following formula (1) showing high mobility can be mentioned.

[0076]

Chemical formula

[0077] Other examples of the organic semiconductor constituting the organic semiconductor single crystal film are shown in the following formula (2) to formula (6).

[0078]

Chemical formula

[0079] In the polythiophene semiconductor represented by formula (2), R1 and R2 are each independently a hydrogen atom or an alkyl group having 4 to 10 carbon atoms. The alkyl group may contain a hetero atom (typically selected from an oxygen atom and a sulfur atom). Further, R1 and R2 can also form a ring together. For reasons of self-aggregation ability, preferably, R1 and R2 are each independently a hydrogen atom or an alkyl group having 5 to 8 carbon atoms. More preferably, R1 and R2 are each independently a hydrogen atom or a hexyl group.

[0080] n represents an integer of 5 to 100. n indicates the average number of thiophene monomer units in the polythiophene semiconductor, that is, the length of the polythiophene chain. From the viewpoint of forming a single crystal film, n is preferably 50 or less.

[0081] [Chemistry]

[0082] In formula (3), R3, R4, R5 and R6 are each independently a hydrogen atom or an alkyl group having 1 to 14 carbon atoms. The alkyl group may contain a heteroatom (typically selected from an oxygen atom and a sulfur atom), and a hydrogen atom in the alkyl group may be substituted with a substituent such as a halogen atom. For reasons of self-aggregation ability, it is preferable that R4 = R5, and it is preferable that R3 = R6. From the viewpoint of solubility, preferably, R4 and R5 are hydrogen atoms, and R3 and R6 are each independently an alkyl group having 1 to 14 carbon atoms, or R3 and R6 are hydrogen atoms, and R4 and R5 are each independently an alkyl group having 1 to 14 carbon atoms. More preferably, R3 and R6 are hydrogen atoms, and R4 and R5 are each independently an alkyl group having 1 to 14 carbon atoms. For reasons of self-aggregation ability, the preferable carbon number of the alkyl group is 4 to 12, and more preferably 6 to 10.

[0083] [Chemistry]

[0084] In formula (4), R7, R8, R9, and R10 are each independently a hydrogen atom or an alkyl group having 1 to 14 carbon atoms. The alkyl group may contain a heteroatom (typically selected from an oxygen atom and a sulfur atom), and a hydrogen atom in the alkyl group may be substituted with a substituent such as a halogen atom. For reasons of self-aggregation ability, it is preferable that R7 = R9, and it is preferable that R8 = R10. From the viewpoint of solubility, preferably, R7 and R9 are hydrogen atoms, and R8 and R10 are each independently an alkyl group having 1 to 14 carbon atoms, or R8 and R10 are hydrogen atoms, and R7 and R9 are each independently an alkyl group having 1 to 14 carbon atoms. More preferably, R8 and R10 are hydrogen atoms, and R7 and R9 are each independently an alkyl group having 1 to 14 carbon atoms. For reasons of self-aggregation ability, the preferable number of carbon atoms of the alkyl group is 6 to 13, and more preferably 8 to 10.

[0085]

Chemical formula

[0086] In formula (5), R11, R12, R13, and R14 are each independently a hydrogen atom or an alkyl group having 1 to 14 carbon atoms. The alkyl group may contain a heteroatom (typically selected from an oxygen atom and a sulfur atom), and a hydrogen atom in the alkyl group may be substituted with a substituent such as a halogen atom. For reasons of self-aggregation ability, it is preferable that R11 = R13, and it is preferable that R12 = R14. From the viewpoint of solubility, preferably, R11 and R13 are hydrogen atoms, and R12 and R14 are each independently an alkyl group having 1 to 14 carbon atoms, or R12 and R14 are hydrogen atoms, and R11 and R13 are each independently an alkyl group having 1 to 14 carbon atoms. More preferably, R12 and R14 are hydrogen atoms, and R11 and R13 are each independently an alkyl group having 1 to 14 carbon atoms. For reasons of self-aggregation ability, the preferable number of carbon atoms of the alkyl group is 5 to 12, and more preferably 8 to 10.

[0087]

Chemical formula

[0088] In formula (6), R15, R16, R17, and R18 are each independently a hydrogen atom or an alkyl group having 1 to 14 carbon atoms. The alkyl group may contain a heteroatom (typically selected from oxygen atoms and sulfur atoms), and the hydrogen atoms in the alkyl group may be substituted with substituents such as halogen atoms. For reasons of self-aggregation ability, it is preferable that R15 = R17, and it is preferable that R16 = R18. From the perspective of solubility, preferably, R16 and R18 are hydrogen atoms, and R15 and R17 are each independently an alkyl group having 1 to 14 carbon atoms, or R15 and R17 are hydrogen atoms, and R16 and R18 are each independently an alkyl group having 1 to 14 carbon atoms. More preferably, R16 and R18 are hydrogen atoms, and R15 and R17 are each independently an alkyl group having 1 to 14 carbon atoms. For reasons of self-aggregation ability, the preferable number of carbon atoms of the alkyl group is 5 to 12, and more preferably 8 to 10.

[0089] Still other examples of the organic semiconductor constituting the organic semiconductor single crystal film are shown in the following formula (7) to the following formula (15). In formula (7) to formula (15), for R, linear alkyl, branched alkyl, fluorinated linear / branched alkyl, triisopropylsilylethynyl, phenyl, etc. can be used.

[0090]

Chemical formula

[0091]

Chemical formula

[0092]

Chemical formula

[0093]

Chemical formula

[0094] [Chemical]

[0095] [Chemical]

[0096] [Chemical]

[0097] [Chemical]

[0098] [Chemical]

[0099] Further examples of organic semiconductors are shown in the following formulas (16) to (19). The n-type organic semiconductors of NDI, PDI, BTDI, and BQQDI shown in formulas (16) to (19) have a twisted stacked structure for each molecular layer although the major axis directions of the main chains are aligned. R can be a straight-chain alkyl, a branched alkyl, a fluorinated straight-chain or branched alkyl, triisopropylsilylethynyl, phenyl, or the like.

[0100] [Chemical]

[0101] [Chemical]

[0102] [Chemical]

[0103]

Chem.

[0104] Another example of the side chain is shown in Formulas (20) to (26). In Formulas (20) to (26), the main chain is BQQDI, an n-type organic semiconductor, but the main chain may also be other than BQQDI, such as NDI or PDI, or the main chain described in Formulas (7) to (15). Formula (20) is an example where the side chain is a phenylethyl group, Formula (21) is an example where the side chain is an aliphatic alkyl group, Formula (22) is an example where the side chain is an aliphatic cyclic alkyl group, Formula (23) is an example where the side chain is an aliphatic chain + cyclic alkyl group, Formula (24) is an example where the side chain is an aromatic group, Formula (26) is an example where the side chain is an alkyl + aromatic (+ halogen) group, and Formula (26) is an example where the side chain is an alkyl + halogen group and a functional group is also added to the BQQDI core.

[0105]

Chem.

[0106]

Chem.

[0107]

Chem.

[0108]

Chem.

[0109]

Chem.

[0110]

Chem.

[0111] [Chemical formula]

[0112] The single crystal film of the organic semiconductor can be confirmed whether it is a single crystal by observing with a transmission electron microscope (TEM).

[0113] When the organic film is an organic semiconductor polymer film, the average film thickness of the organic semiconductor polymer film is 1 nm to 1 μm, preferably 3 to 200 nm. By the average film thickness of the organic semiconductor polymer film being within the above range, good device characteristics can be obtained. The measurement of the average film thickness of the organic semiconductor polymer film can be performed using a stylus type surface profiler or an atomic force microscope.

[0114] The organic semiconductor polymer film preferably has a mobility of 0.005 cm 2 / V·s or more, more preferably 0.05 cm 2 / V·s or more, still more preferably 0.5 cm 2 / V·s or more, even more preferably 5 cm 2 / V·s or more, even more preferably 10 cm 2 / V·s or more. The mobility of the organic semiconductor polymer film can be calculated from the measurement results of the organic field effect transistor.

[0115] When the organic semiconductor polymer film is made into a P-type semiconductor, a P-type polymer semiconductor is dissolved in a solvent, and when it is made into an N-type semiconductor, an N-type polymer semiconductor is dissolved in a solvent. As the P-type polymer semiconductor, those obtained by polymerizing or copolymerizing thiophene, thiadiazole, diketopyrrolopyrrole, etc. can be used. Also, as the N-type polymer semiconductor, those obtained by polymerizing or copolymerizing naphthalenediimide, perylenediimide, thiophene, etc. can be used. As the solvent, dichlorobenzene, toluene, acetonitrile, butyl acetate, fluoroalcohol, etc. can be used.

[0116] The present disclosure also relates to a manufacturing apparatus for a patterned organic film, which includes a stamp placement unit configured to place a stamp having convex and concave portions, a first substrate placement unit configured to be able to place a hydrophilic and water-insoluble first substrate having an organic film on its surface, a second substrate placement unit configured to be able to place a second substrate, a first driving unit configured to be able to move at least one of the first substrate and the stamp so as to press the organic film on the first substrate against the convex portions of the stamp to place the organic film on the convex portions and to separate the first substrate from the organic film placed on the convex portions, a first control unit configured to control the force for pressing the organic film on the first substrate against the convex portions of the stamp, a water or aqueous solution supply unit configured to supply water or an aqueous solution to the interface between the organic film and the first substrate, a second driving unit configured to be able to move at least one of the stamp and the second substrate so as to press the organic film placed on the convex portions of the stamp against the second substrate to place the patterned organic film on the second substrate and to separate the stamp from the patterned organic film placed on the second substrate, and a second control unit configured to control the force for pressing the organic film placed on the convex portions of the stamp against the second substrate.

[0117] FIG. 28 shows a schematic cross-sectional view when a stamp 30, a first substrate 10 and an organic film 20 disposed thereon, and a second substrate 40 are disposed in the manufacturing apparatus 100 of the present disclosure. The stamp 30 is disposed in the stamp placement unit 90, the first substrate 10 is disposed in the first substrate placement unit 91, and the second substrate 40 is disposed in the second substrate placement unit 92. The first substrate placement unit 91 and the second substrate placement unit 92 may be separate or integrated. The first substrate placement unit 91 may be integrated with the manufacturing apparatus 100 or may be separated from the manufacturing apparatus 100. The second substrate placement unit 92 may be integrated with the manufacturing apparatus 100 or may be separated from the manufacturing apparatus 100.

[0118] The manufacturing apparatus 100 includes a first driving unit 93. The first driving unit 93 is configured to move at least one of the first substrate 10 and the stamp 30 so as to press the organic film 20 on the first substrate 10 against the convex portion of the stamp 30 to dispose the organic film 20 on the convex portion and separate the first substrate 10 from the organic film disposed on the convex portion. FIG. 28 is an example in which the first driving unit 93 is capable of moving both the first substrate 10 and the stamp 30.

[0119] The manufacturing apparatus 100 includes a first control unit 94 configured to control the force with which the first driving unit 93 presses the organic film 20 on the first substrate 10 against the convex portion of the stamp 30.

[0120] The manufacturing apparatus 100 includes a supply unit 80 for water or an aqueous solution configured to supply water or an aqueous solution to the interface between the organic film 20 and the first substrate 10.

[0121] The manufacturing apparatus 100 includes a second driving unit 95. The second driving unit 95 is configured to move at least one of the stamp 30 and the second substrate 40 so as to press the organic film on the convex portion of the stamp 30 against the second substrate 40 to dispose the patterned organic film on the second substrate 40 and separate the stamp from the patterned organic film disposed on the second substrate 40. FIG. 28 is an example in which the second driving unit 95 is capable of moving both the stamp 30 and the second substrate 40.

[0122] The manufacturing apparatus 100 includes a second control unit 96 configured to control the force with which the second driving unit 95 presses the organic film on the convex portion of the stamp 30 against the second substrate 40.

[0123] At least one of the stamp placement unit 90, the first substrate placement unit 91, and the second substrate placement unit 92 is movable in a direction perpendicular to the pressing direction. At least one of the first driving unit 93 and the second driving unit 95 may be a driving unit that moves at least one of the stamp placement unit 90, the first substrate placement unit 91, and the second substrate placement unit 92, or the manufacturing apparatus 100 may include, separately from the first driving unit 93 and the second driving unit 95, a driving unit that moves at least one of the stamp placement unit 90, the first substrate placement unit 91, and the second substrate placement unit 92. The first driving unit 93 and the second driving unit 95 may be integrated or separate. The first control unit 94 and the second control unit 96 may be integrated or separate.

[0124] Preferably, the first control unit is configured to control the distribution of the pressing force in the plane of the organic film when pressing the organic film on the first substrate against the convex portion. Preferably, the second control unit is configured to control the distribution of the pressing force in the plane of the organic film when pressing the organic film disposed on the convex portion of the stamp against the second substrate.

[0125] Preferably, the manufacturing apparatus 100 includes an amount adjustment unit for water or an aqueous solution that is configured to be able to adjust the amount of water or an aqueous solution supplied by the supply unit for water or an aqueous solution. The amount adjustment unit for water or an aqueous solution may automatically adjust the valve opening degree in accordance with the flow rate set value.

[0126] Preferably, the manufacturing apparatus 100 includes a supply position adjustment unit that recognizes the position of the interface between the organic film that supplies water or an aqueous solution and the first substrate and is capable of adjusting the position of the water or an aqueous solution supplied by the supply unit for water or an aqueous solution. The recognition of the position of the interface between the organic film and the first substrate may be performed by image processing such as binarization processing using a camera.

[0127] Preferably, the manufacturing apparatus 100 includes a first alignment unit that controls the position where the organic film on the first substrate is pressed against the convex portion of the stamp. The alignment in the first alignment unit can be alignment based on the edge of the first substrate or the edge of the organic film and the edge of the stamp, alignment based on the markings on the first substrate or the organic film and the markings on the stamp, a combination thereof, and the like. Detection of the reference position can be detection by image processing such as binarization, mechanical contact detection, and the like.

[0128] Preferably, the manufacturing apparatus 100 includes a second alignment unit that controls the position where the organic film on the convex portion of the stamp is pressed against the second substrate. The alignment in the second alignment unit can be alignment based on the edge of the stamp or the edge of the organic film and the edge of the second substrate, alignment based on the markings on the stamp or the organic film and the markings on the second substrate, a combination thereof, and the like. Detection of the reference position can be detection by image processing such as binarization, mechanical contact detection, and the like. The first alignment unit and the second alignment unit may be common. The first alignment unit and the second alignment unit may include the configuration of a conventional alignment apparatus such as a camera, a processing unit, a storage unit, a communication unit capable of transmitting and receiving data, and the like.

[0129] FIG. 39 shows an external photograph of an example of the manufacturing apparatus of the present disclosure. The manufacturing apparatus includes a stamp placement unit 90, a first substrate placement unit 91, a second substrate placement unit 92, and an alignment camera. The four alignment cameras provided in the manufacturing apparatus of FIG. 39 function as the cameras of the first alignment unit and the second alignment unit.

[0130] Regarding the configuration of the organic film in the manufacturing apparatus of the present disclosure, the content regarding the organic film in the manufacturing method of the patterned organic film described above can be applied. Regarding the configurations of the stamp, the first substrate, and the second substrate in the manufacturing apparatus of the present disclosure, the content regarding the stamp, the first substrate, and the second substrate in the manufacturing method of the patterned organic film described above can be applied respectively.

[0131] The present disclosure also targets an organic semiconductor device including a substrate and a patterned organic film on the substrate, where the organic film is hydrophobic and at least one of the organic film and the substrate is an organic semiconductor.

[0132] The substrate in the organic semiconductor device preferably has no damage caused by patterning of the organic film.

[0133] FIG. 24 shows a cross-sectional schematic view of a substrate 40 and a patterned organic film 21 on the substrate included in the organic semiconductor device of the present disclosure. Using the substrate and the patterned organic film on the substrate included in the organic semiconductor device of the present disclosure, a field-effect transistor, for example, the bottom gate / top contact type field-effect transistor illustrated in FIGS. 12 and 17, can be fabricated.

[0134] Having no damage caused by patterning of the organic film means having no damage caused by patterning of the organic film on the substrate conventionally performed. When attempting to pattern the organic film in the prior art, patterning is performed on the substrate, but the substrate surface may be altered or decomposed by plasma treatment, laser etching, etching solvent treatment, etc. when etching the organic film. On the other hand, in the organic semiconductor device of the present disclosure, as described regarding the manufacturing method of the patterned organic film, since the patterned organic film is transferred onto the substrate, the substrate in the organic semiconductor device of the present disclosure does not substantially undergo alteration or decomposition due to patterning of the organic film.

[0135] The fact that substantially no deterioration or decomposition occurs means that the substrate is not substantially dissolved or swollen by photoresists, developers, etching solutions, stripping solutions, etc. used during the photolithography process of organic films in the prior art, that the substrate surface is not deteriorated or decomposed by plasma treatment or the like during the etching of organic films in the prior art, that the substrate does not expand or contract by heat treatment or the like during the photolithography process of organic films in the prior art, and the like. Preferably, the patterned organic film also has no damage caused by the patterning of the organic film. That is, preferably, for the patterned organic film as well, substantially no such deterioration or decomposition as described above occurs due to the patterning of the organic film.

[0136] The organic semiconductor device of the present disclosure preferably includes electrodes on at least a part between the substrate and the organic film, at least a part on the side opposite to the substrate with respect to the organic film, or both of them. FIG. 25 shows a cross-sectional schematic view of an organic semiconductor device including an electrode 60 between a substrate 40 and an organic film 21. FIG. 27 shows a cross-sectional schematic view of an organic semiconductor device including an electrode 60 on the side opposite to the substrate 40 with respect to the organic film 21. The thickness of the electrode is preferably 10 to 50 nm. FIGS. 29 to 32 show representative transistor structures that the organic semiconductor device of the present disclosure can have. FIG. 29 is a cross-sectional schematic view of a top gate / top contact structure. FIG. 30 is a cross-sectional schematic view of a top gate / bottom contact structure. FIG. 31 is a cross-sectional schematic view of a bottom gate / top contact structure. FIG. 32 is a cross-sectional schematic view of a bottom gate / bottom contact structure. The structure that the organic semiconductor device of the present disclosure can have is not limited to the configurations shown in FIGS. 29 to 32. For example, a layer such as a sealing film may further exist on the uppermost layer of the structures shown in FIGS. 29 to 32.

[0137] The organic semiconductor device of the present disclosure preferably includes a space between the substrate, the organic film, and the electrode. FIG. 26 shows a cross-sectional schematic view of an organic semiconductor device including a space 70 between a substrate 40, an organic film 21, and an electrode 60. By forming a bridging structure as shown in FIG. 26, it can function as an insulating layer of the transistor.

[0138] The width of the space is preferably 500 nm to 5 μm.

[0139] The organic semiconductor device of the present disclosure can be an organic EL (electroluminescence) element, an organic solar cell element, an organic photoelectric conversion element, an organic transistor element, an organic field effect transistor element, an organic complementary semiconductor device (organic CMOS or organic CMOS logic circuit) including a p-type organic transistor and an n-type organic transistor, an inorganic-organic hybrid complementary semiconductor device including an organic transistor and an inorganic transistor, etc.

[0140] Regarding the configuration of the organic film in the organic semiconductor device of the present disclosure, the content regarding the organic film in the manufacturing method of the above-patterned organic film can be applied. Regarding the configuration of the substrate in the organic semiconductor device of the present disclosure, the content regarding the second substrate in the manufacturing method of the above-patterned organic film can be applied.

[0141] An integrated circuit can be obtained using the organic semiconductor device of the present disclosure. The integrated circuit may preferably include 10 or more transistors, more preferably 100 or more transistors, still more preferably 1000 or more transistors, and even more preferably 10000 or more transistors. The integrated circuit includes logic gates such as AND, OR, NOT, NAND, NOR, XOR, and XNOR. As an example of the integrated circuit, a D flip-flop (DFF) circuit, which is a type of sequential circuit that stores past inputs and determines outputs, can be mentioned.

Example

[0142] (Example 1) (Mold fabrication) The Eagle glass substrate was subjected to a hydrophilic treatment by UV / O treatment for 10 minutes. Next, SU-8, which is a photoresist, was spin-coated on the hydrophilic-treated glass substrate. 3

[0143] The glass substrate spin-coated with SU-8 was heat-treated at 95°C for 6 minutes to mask a predetermined pattern and subjected to UV exposure, followed by heat treatment at 95°C for 3 minutes. Subsequently, SU-8 was developed for 3 minutes using propylene glycol monomethyl acetate (PGMEA) and heat-treated at 170°C for 30 minutes.

[0144] On the glass substrate on which SU-8 was developed and heat-treated, F-SAM treatment was performed by a vapor phase method for 3.5 hours to form a self-assembled monolayer, and a glass mold having a photoresist with a self-assembled monolayer on the surface was fabricated.

[0145] (Fabrication of PDMS stamp) The PDMS solution (main agent: SIM-360, hardener: CAT-360, manufactured by Shin-Etsu Chemical Co., Ltd.) was stirred and degassed using a bubble remover Rentaro. The stirred and degassed PDMS solution was dropped onto the fabricated mold, an Eagle glass substrate was placed on the PDMS, weights were placed on the Eagle glass substrate, and it was left standing, and the PDMS was thermally cured at 150°C for 30 minutes.

[0146] Subsequently, the mold was peeled off from the PDMS to fabricate a stamp. The fabricated stamp had 100 convex portions, the width of the convex portions was 500 μm, the length of the convex portions was 700 μm, the distance between adjacent convex portions was 500 μm, and the distance between the uppermost part of the convex portion and the lowermost part of the concave portion was 7 μm.

[0147] (Fabrication of patterned organic semiconductor film) As the organic semiconductor, the following formula (27) showing high mobility:

Chemical formula

[0148] As the first substrate, the surface was treated with UV / O 3An Eagle glass substrate hydrophilized by treatment (hereinafter also referred to as the glass substrate) was prepared. The prepared organic semiconductor solution was applied onto the glass substrate heated to 90 °C by the continuous edge casting method, and an organic semiconductor single crystal film with an average thickness of 12 nm and an area of 80 cm 2 and a single domain area of 1000 mm 2 was formed. The contact angle of water on the surface of the organic semiconductor single crystal film was 108 degrees.

[0149] As the second substrate, a parylene / SiO 2 / n-doped Si substrate on which parylene (diX-SR (registered trademark)) was formed was prepared.

[0150] Using the manufacturing apparatus schematically shown in FIG. 28, a patterned organic semiconductor single crystal film was fabricated. A stamp was placed on the stamp placement section, the first substrate on which an organic semiconductor single crystal film (hereinafter also referred to as the semiconductor film) was formed was placed on the first substrate placement section, and the second substrate was placed on the second substrate placement section.

[0151] As shown in FIG. 1, the first substrate was pressed against the fabricated stamp so that the convex portion of the stamp was in contact with the semiconductor film. As shown in FIG. 2, after pressing the first substrate against the stamp with a pressure of 50 kPa per unit area of the convex portion of the stamp, water was dropped onto the interface between the first substrate and the semiconductor film. As shown in FIG. 3, the semiconductor film was placed on the convex portion of the stamp, and the first substrate was separated from the semiconductor film placed on the convex portion. FIG. 9 shows a polarized light microscope image of the semiconductor film transferred onto the PDMS stamp. In FIG. 9, the semiconductor film is transferred onto both the convex and concave portions of the PDMS stamp. FIG. 10 shows a scanning electron microscope (SEM) image of the semiconductor film transferred onto the convex and concave portions of the PDMS stamp observed obliquely from above.

[0152] As shown in Fig. 4, a stamp was pressed against a second substrate at a pressure of 100 kPa per unit area of the convex portion of the stamp so that the semiconductor film transferred onto the convex portion of the stamp was in contact with the parylene on the second substrate, and the patterned semiconductor film was disposed on the second substrate. Then, the stamp was separated from the semiconductor film disposed on the second substrate, and a patterned organic semiconductor single crystal film 21 schematically shown in Fig. 5 was obtained.

[0153] Fig. 11 shows a polarized light microscopic image of the transferred organic semiconductor film 21 observed from above. The obtained organic semiconductor single crystal film was neatly patterned, had a thickness of 8 nm, a width of 500 μm, and the interval between semiconductor films was 500 μm, with 100 patterns.

[0154] As shown in Fig. 12, on the parylene / SiO 2 / n-doped Si substrate, on the organic semiconductor single crystal film of C 9 -DNBDT-NW, an Au electrode with a length of 0.4 mm, a width of 2 mm, and a height of 40 nm was formed by vacuum evaporation as an S / D electrode (source / drain electrode) using a metal mask, and a bottom gate top contact (BGTC) type organic field effect transistor (OFET) was fabricated. The channel length L was 100 μm, and the channel width W was 500 μm. The channel length is the distance between two electrodes (S / D electrodes). Fig. 13 shows a polarized light microscopic image of the fabricated BGTC type OFET observed from above.

[0155] Fig. 14 shows a graph of transfer characteristics representing the relationship between the gate voltage and the drain current in the saturation region of the fabricated BGTC type OFET. Fig. 15 shows a graph of transfer characteristics representing the relationship between the gate voltage and the drain current in the linear region. Fig. 16 shows a graph of output characteristics representing the relationship between the drain voltage and the drain current with respect to the gate voltage. The mobility in the saturation region was 10.7 cm 2 / V·s, and the mobility in the linear region was 9.92 cm 2 / V·s, indicating a very high mobility.

[0156] (Example 2) As the second substrate, instead of parylene / SiO 2 / n-doped Si substrate, an organic semiconductor single crystal film patterned in the same manner as in Example 1 was obtained except that CYTOP (registered trademark) / SiO 2 / n-doped Si substrate was used.

[0157] The obtained organic semiconductor single crystal film 21 was neatly patterned, with a thickness of 8 nm, a width of 500 μm, and a pattern of 100 with a spacing of 500 μm between semiconductor films.

[0158] As shown in Fig. 17, on the organic semiconductor single crystal film of C 2 -DNBDT-NW disposed on a CYTOP (registered trademark) / SiO 9 / n-doped Si substrate, an Au electrode with a length of 0.4 mm, a width of 2 mm, and a height of 40 nm was formed by vacuum evaporation as an S / D electrode (source / drain electrode) using a metal mask, and a bottom gate top contact (BGTC) type organic field effect transistor (OFET) was fabricated. The channel length L was 100 μm and the channel width W was 500 μm. Fig. 18 shows a polarized light microscope image observed from the top surface of the fabricated BGTC type OFET.

[0159] Fig. 19 shows a graph of transfer characteristics representing the relationship between gate voltage and drain current in the saturation region of the fabricated BGTC type OFET, Fig. 20 shows a graph of transfer characteristics representing the relationship between gate voltage and drain current in the linear region, and Fig. 21 shows a graph of output characteristics representing the relationship between drain voltage and drain current with respect to gate voltage. The mobility in the saturation region was 7.18 cm 2 / V·s, and the mobility in the linear region was 16.8 cm 2 / V·s, indicating a very large mobility.

[0160] (Example 3) As the second substrate, instead of parylene / SiO 2 / n-doped Si substrate, trimethoxy(2-phenylethyl)silane (β-PTS) / SiO 2An organic semiconductor single crystal film patterned in the same manner as in Example 1 was obtained, except that an n-doped Si substrate was used and stamps with convex widths of 20 μm, 40 μm, 50 μm, 100 μm, and 150 μm were used.

[0161] Fig. 22 shows a polarized light microscope image of the organic semiconductor single crystal film 21 transferred onto the second substrate, observed from above. The obtained organic semiconductor single crystal film was neatly patterned, with a thickness of 8 nm, widths of 15 μm, 35 μm, 45 μm, 95 μm, and 145 μm, a length of 800 μm, and a pattern with a spacing of 100 μm between the semiconductor films.

[0162] (Example 4) As the second substrate, parylene / SiO 2 / n-doped Si substrate was replaced with β-PTS / SiO 2 / n-doped Si substrate, and an organic semiconductor single crystal film patterned in the same manner as in Example 1 was obtained, except that stamps with a spacing of 5 μm, 10 μm, 20 μm, and 30 μm between the convex portions were used.

[0163] Fig. 23 shows a polarized light microscope image of the organic semiconductor single crystal film 21 transferred onto the second substrate, observed from above. The obtained organic semiconductor single crystal film was neatly patterned, with a thickness of 8 nm, a width of 200 μm, a length of 800 μm, and a pattern with spacings of 10 μm, 15 μm, 25 μm, and 35 μm between the semiconductor films.

[0164] (Example 5) As the second substrate, a 4-inch diameter parylene / SiO 2 / n-doped Si substrate was used, and an organic semiconductor single crystal film patterned with a thickness of 4 - 20 nm, a width of 50 - 9000 μm, a length of 10 - 1300 μm, and a spacing of 2 - 10000 μm between the semiconductor films was formed. 4700 such films were obtained in the same manner as in Example 1. Fig. 33 shows an exterior photograph of a 4-inch wafer having the obtained patterned semiconductor organic film.

[0165] (Example 6) Using an Si substrate as the second substrate, 64 organic semiconductor single crystal films, each being a 700 μm × 500 μm organic semiconductor single crystal film patterned as an 8 × 8 array at intervals of 500 μm in the horizontal direction and 300 μm in the vertical direction, were formed on the Si substrate. A patterned organic semiconductor single crystal film was obtained in the same manner as in Example 1, except for the above.

[0166] Fig. 34 shows a laser confocal microscope image of the obtained 8 × 8 array of aligned organic semiconductor single crystal films. The portion surrounded by the square frame is one 700 μm × 500 μm organic semiconductor single crystal film, and the organic semiconductor single crystal films are aligned in an 8 × 8 pattern throughout the microscope image.

[0167] Fig. 35 shows the measurement results of in-plane X-ray diffraction (SmartLab, Rigaku Corporation, radiation source CuKα (wavelength λ = 1.54056 Å)) obtained by rotating the substrate holding the organic semiconductor single crystal film 360 degrees while irradiating the portion surrounded by the broken line in Fig. 34 with X-rays. One diffraction peak was observed at a period of 180 degrees, and it was found that substantially all of the organic semiconductor single crystal films within the broken line portion were single crystal films oriented in substantially the same direction. It was suggested that the crystal orientations of the organic semiconductor single crystal films located in the portion surrounded by the broken line in Fig. 34 were included within ±1 degree. Fig. 36 shows an enlarged view of the 020 diffraction line of the C 9 -DNBDT-NW organic semiconductor single crystal. When the full width at half maximum of the peak in Fig. 36 was calculated, it was 0.535 degrees, and a very sharp peak was obtained.

[0168] (Example 7) (Fabrication of n-type TFT) As the substrate, a polyethylene naphthalate (PEN) substrate with a thickness of 125 μm (Teonex Q65HA, Teijin DuPont Films Co., Ltd.) was used. After peeling off the protective film from the PEN substrate, as a pretreatment, it was heated on a hot plate at 150 °C for 3 hours, and ultrasonic cleaning was performed with acetone and 2-propanol for 10 minutes each.

[0169] On the entire surface of the PEN substrate that had been heat-treated and cleaned, an Al film with a thickness of 30 nm was formed by electron beam evaporation. Patterning of the gate electrode was performed on the formed Al film by a photolithography process. The photolithography process was carried out in the following procedure.

[0170] On the Al film, AZ 5214 E (MicroChemicals), a positive photoresist, was spin-coated under the conditions of 1 second at a slope, 5 seconds at 500 rpm, 40 seconds at 3000 rpm, and 2 seconds at 5000 rpm, and the spin-coated PEN substrate was heat-treated on a hot plate at 105 °C for 70 seconds.

[0171] The PEN substrate spin-coated with AZ 5214 E was irradiated with ultraviolet light (λ = 375 nm) using a maskless aligner (MLA 150 Maskless Aligner, Heidelberg Instruments), and then developed by immersing it in a developer (NMD-3, 2.38%, Tokyo Ohka Kogyo Co., Ltd.) and ultrapure water in sequence.

[0172] The PEN substrate with the developed resist was immersed in a mixed acid Al etching solution (Kanto Chemical Co., Inc.) for wet etching of the Al film, and the resist was peeled off using AZ (registered trademark) 100 Remover. The resist residue was removed by 5 minutes of UV / O 3 treatment, and a parylene (diX-SR (registered trademark)) with a thickness of 120 nm was deposited by CVD method to form a gate insulating film.

[0173] In the same manner as in Example 1, a 10 cm square PDMS stamp having a pattern for an n-type semiconductor was fabricated.

[0174] As the organic semiconductor, a powder of the n-type organic semiconductor PhC of the above formula (20) 2 -BQQDI was prepared, and in the same manner as in Example 1, an organic semiconductor solution was prepared, and on the first substrate, the average thickness was 10 nm and the area was 15 cm 2 , and a single-domain organic semiconductor single crystal film with an area of 10 mm 2 was formed.

[0175] Using the manufacturing apparatus shown in FIG. 39, a patterned organic semiconductor single crystal film was fabricated. The fabricated PDMS stamp was placed in the stamp placement section, the first substrate on which the organic semiconductor single crystal film (hereinafter also referred to as the semiconductor film) was formed was placed in the first substrate placement section, and the second substrate was placed in the second substrate placement section.

[0176] The first substrate was pressed against the fabricated stamp at a pressure of 10 kPa per unit area of the convex portion of the stamp so that the convex portion of the stamp was in contact with the semiconductor film. Then, after pressing the first substrate against the stamp, an aqueous ethanol solution of 30 wt% was dropped onto the interface between the first substrate and the semiconductor film, the semiconductor film was placed on the convex portion of the stamp, and the first substrate was separated from the semiconductor film placed on the convex portion.

[0177] In the second substrate placement section of FIG. 39, a PEN substrate on which a gate electrode and a gate insulating film were formed was placed, and a PDMS stamp on which the semiconductor film was transferred was placed in the stamp placement section.

[0178] Using cameras installed at the four corners of the stamp adsorption stage, while observing the alignment marks arranged on each of the gate electrode layer and the PDMS stamp, the position of the second substrate was moved to an appropriate position. Next, while applying a load of 50 kPa per unit area of the convex portion of the stamp using a load cell, the stamp was pressed against the second substrate for 30 seconds so that the semiconductor film transferred onto the convex portion of the PDMS stamp was in contact with the parylene on the second substrate, and the patterned semiconductor film was placed on the second substrate. Then, the stamp was separated from the semiconductor film placed on the second substrate, and a patterned organic semiconductor single crystal film 21 was obtained. Drying was performed in a vacuum oven at 80 °C for 10 hours. The obtained organic semiconductor single crystal film was neatly patterned, with a thickness of 6 - 20 nm, a width of 250 μm, a length of 120 - 200 μm, and the distance between semiconductor films was 20 - 200 μm, forming 264 patterns.

[0179] Next, Au was vacuum-evaporated to a thickness of 50 nm over the entire surface, and patterning of the S / D electrodes was performed by a photolithography process to fabricate a bottom gate top contact (BGTC) type organic field effect transistor (OFET). Fig. 37 shows a cross-sectional schematic view of the obtained BGTC type OFET.

[0180] Fig. 38 shows graphs of transfer characteristics representing the relationship between gate voltage and drain current in the saturation region of the fabricated BGTC type OFET, graphs of transfer characteristics representing the relationship between gate voltage and drain current in the linear region, and a graph of output characteristics representing the relationship between drain voltage and drain current with respect to gate voltage. The mobility in the saturation region was 0.18 cm 2 / V·s, and the mobility in the linear region was 0.22 cm 2 / V·s.

[0181] (Example 8) Using stamps with convex widths of 20 μm, 40 μm, 50 μm, 100 μm, 150 μm, and 200 μm, an organic semiconductor single crystal film patterned in the same manner as in Example 3 was obtained, except that the pressing pressure of the stamp onto the first substrate was 10 kPa per unit area of the convex portion of the stamp, and the pressing pressure of the stamp onto the second substrate was 50 kPa per unit area of the convex portion of the stamp.

[0182] Figure 40 shows a polarized light microscope image of the organic semiconductor single crystal film 21 transferred onto the second substrate, observed from above. The obtained organic semiconductor single crystal film was neatly patterned, with a thickness of 12 nm, a width of 20 μm, 40 μm, 50 μm, 100 μm, 150 μm, and 200 μm, a length of 800 μm, and a pattern with a spacing of 100 μm between the semiconductor films.

[0183] (Example 9) Using stamps with a spacing of 1 μm, 2 μm, 5 μm, 10 μm, and 20 μm between the convex portions, an organic semiconductor single crystal film patterned in the same manner as in Example 4 was obtained, except that the pressing pressure of the stamp onto the first substrate was 10 kPa per unit area of the convex portion of the stamp, and the pressing pressure of the stamp onto the second substrate was 50 kPa per unit area of the convex portion of the stamp.

[0184] Figure 41 shows a polarized light microscope image of the organic semiconductor single crystal film 21 transferred onto the second substrate, observed from above. The obtained organic semiconductor single crystal film was neatly patterned, with a thickness of 12 nm, a width of 800 μm, a length of 200 μm, and a pattern with a spacing of 1 μm, 2 μm, 5 μm, 10 μm, and 20 μm between the semiconductor films.

[0185] (Example 10) Using stamps with convex portions of 60 μm square, 80 μm square, 100 μm square, 300 μm square, and 500 μm square, an organic semiconductor single crystal film patterned in the same manner as in Example 4 was obtained, except that the pressing pressure of the stamp onto the first substrate was 10 kPa per unit area of the convex portion of the stamp, and the pressing pressure of the stamp onto the second substrate was 50 kPa per unit area of the convex portion of the stamp.

[0186] Figure 42 shows a polarized light microscope image of the organic semiconductor single crystal film 21 transferred onto the second substrate, observed from above. The obtained organic semiconductor single crystal film was neatly patterned, had a thickness of 8 - 12 nm, and had patterns of 60 μm square, 80 μm square, 100 μm square, 300 μm square, and 500 μm square.

[0187] (Example 11) An organic semiconductor single crystal film patterned in the same manner as in Example 4 was obtained, except that stamps with convex portions of 30 μm square, 40 μm square, and 50 μm square were used, and the pressing pressure of the stamp onto the first substrate was 10 kPa per unit area of the convex portion of the stamp, and the pressing pressure of the stamp onto the second substrate was 50 kPa per unit area of the convex portion of the stamp.

[0188] Figure 43 shows a polarized light microscope image of the organic semiconductor single crystal film 21 transferred onto the second substrate, observed from above. The obtained organic semiconductor single crystal film was neatly patterned, had a thickness of 8 - 12 nm, and had patterns of 30 μm square, 40 μm square, and 50 μm square.

[0189] (Example 12) (Fabrication of CMOS Logic Circuits: NOT, NOR, NAND, and DFF Circuits) In the same manner as in Example 7, an Al gate electrode with a thickness of 30 nm and a gate insulating film of parylene (diX - SR (registered trademark)) with a thickness of 120 nm were formed on a PEN substrate.

[0190] On the gate insulating film, in the same manner as in Example 7, a p - type organic semiconductor C 9 -DNBDT - NW film was transferred with a p - type stamp, and then, on the same layer, an n - type organic semiconductor PhC 2The -BQQDI film was transferred using an n-type stamp. The obtained p-type organic semiconductor single-crystal film was neatly patterned and had a thickness of 8 - 12 nm, a width of 80 μm, and a length of 124 - 200 μm. The obtained n-type organic semiconductor single-crystal film was also neatly patterned and had a thickness of 10 - 12 nm, a width of 250 μm, and a length of 120 - 200 μm.

[0191] Using a YAG laser, the gate insulating film was etched to expose some of the gate electrodes (Via (Vertical Interconnect Access) openings). Then, 50 nm of Au was deposited over the entire surface to electrically connect the exposed gate electrodes and the source / drain electrode layer. Next, in the same manner as in Example 7, p-type organic semiconductor C 9 -DNBDT-NW film and on the n-type organic semiconductor PhC 2 Source and drain electrodes of Au were patterned on the -BQQDI film to fabricate an organic complementary semiconductor device comprising a p-type organic transistor (p-TFT) and an n-type organic transistor (n-TFT). The L / W of the p-TFT was 12 μm / 80 μm, and the L / W of the n-TFT was 8 μm / 500 μm. Fig. 48 shows a cross-sectional schematic diagram of the fabricated device.

[0192] As shown in Fig. 49, a D flip-flop (DFF) circuit using NOT, NOR, NAND, and 2-to-1 selectors composed of the organic complementary semiconductor devices shown in Fig. 48 was fabricated within an area of 3 mm × 5 mm on a flexible PEN substrate. Fig. 44 shows a circuit diagram of the fabricated DFF circuit.

[0193] Fig. 45 shows a truth table of a negative edge-triggered DFF. Fig. 46 shows V DDShows the operation confirmation results at 10V. As shown in Fig. 46, the Data signal is read into the output Q only at the timing when the Clock signal changes from H to L, and it was confirmed that the output Q holds the Data signal without being reflected at the timing of switching from L to H or other timings. Also, the output QB was obtained as a signal obtained by inverting the output Q. Therefore, it can be said that the fabrication of a negative edge-triggered DFF on the PEN substrate, which is a flexible substrate, was successful.

[0194] Furthermore, when the element was operated at V DD = 5V, as shown in Fig. 47, an output with a voltage of 5V when H was obtained with the same waveform as in Fig. 46, and it was possible to drive it at a low voltage.

Explanation of symbols

[0195] 10 First substrate 20 Organic film 21 Patterned organic film 22 Organic film on the recess 30 Stamp 31 Convex part of the stamp 32 Concave part of the stamp 33 Liquid stamp material 40 Second substrate 42 Hydrophobic film 50 Mold 52 Substrate for mold fabrication 54 Photoresist 56 Release layer 57 Support substrate 58 Weight 60 Electrode 70 Space 80 Water or aqueous solution feeder, or water or aqueous solution supply part 82 Water or aqueous solution 90 Stamp placement part 91 First substrate placement part 92 Second substrate placement part 93 First drive part 94 Control part 95 Second drive part 96 Second control part 100 manufacturing apparatus

Claims

1. Forming a hydrophobic organic film on a hydrophilic and water-insoluble first substrate using a coating method; Pressing the organic film formed on the first substrate against the convex portions of a stamp having convex and concave portions; Applying water or an aqueous solution to the interface between the first substrate and the organic film to transfer the organic film to the convex portions; and Pressing the organic film transferred to the convex portions against a second substrate to transfer the organic film to the second substrate and obtain a patterned organic film, comprising: wherein at least one of the organic film and the second substrate is an organic semiconductor, A method for manufacturing a patterned organic film.

2. The manufacturing method according to claim 1, wherein the distance between the uppermost part of the convex portion and the lowermost part of the concave portion is 2 to 100 μm.

3. The manufacturing method according to claim 1 or 2, wherein the patterned organic film includes 10 or more organic films, each organic film having a thickness of 2 nm or more, a width of 500 nm or more, and a length of 500 nm or more, and the interval between adjacent organic films is 1 μm or more.

4. A stamp placement unit configured to place a stamp having convex and concave portions; A first substrate placement unit configured to be able to place a hydrophilic and water-insoluble first substrate having an organic film on its surface; A second substrate placement unit configured to be able to place a second substrate; A first driving unit configured to be able to move at least one of the first substrate and the stamp so as to press the organic film on the first substrate against the convex portions of the stamp to place the organic film on the convex portions and separate the first substrate from the organic film placed on the convex portions; A first control unit configured to control the force for pressing the organic film on the first substrate against the convex portions of the stamp; A water or aqueous solution supply unit configured to supply water or an aqueous solution to the interface between the organic film and the first substrate; A second driving unit configured to be able to move at least one of the stamp and the second substrate so as to press the organic film placed on the convex portions of the stamp against the second substrate to place the patterned organic film on the second substrate and separate the stamp from the patterned organic film placed on the second substrate; and A second control unit configured to control the force for pressing the organic film placed on the convex portions of the stamp against the second substrate, A manufacturing apparatus for a patterned organic film.

5. The manufacturing apparatus according to claim 4, wherein the first control unit is configured to control the distribution of the pressing force in the plane of the organic film when pressing the organic film against the convex portion.

6. The manufacturing apparatus according to claim 4 or 5, wherein the second control unit is configured to control the distribution of the pressing force in the plane of the organic film when pressing the organic film against the second substrate.

7. The manufacturing apparatus according to any one of claims 4 to 6, further comprising a water or aqueous solution amount adjustment unit configured to be able to adjust the amount of water or aqueous solution supplied by the water or aqueous solution supply unit.

8. The manufacturing apparatus according to any one of claims 4 to 7, further comprising a supply position adjustment unit configured to recognize the position of the interface for supplying the water or aqueous solution and adjust the position of the water or aqueous solution supplied by the water or aqueous solution supply unit.

9. The manufacturing apparatus according to any one of claims 4 to 8, further comprising a first alignment unit configured to control the position where the organic film on the first substrate is pressed against the convex portion of the stamp.

10. The manufacturing apparatus according to any one of claims 4 to 9, further comprising a second alignment unit configured to control the position where the organic film on the convex portion of the stamp is pressed against the second substrate.

11. A substrate, and a patterned organic film on the substrate are included, the organic film is hydrophobic, at least one of the organic film and the substrate is an organic semiconductor, the patterned organic film is formed by a coating method to form a hydrophobic organic film on a hydrophilic and water-insoluble first substrate, pressing the organic film formed on the first substrate against the convex portion of a stamp having convex and concave portions, applying water or an aqueous solution to the interface between the first substrate and the organic film to transfer the organic film to the convex portion, and pressing the organic film transferred to the convex portion against a second substrate to transfer the organic film to the second substrate is obtained by the organic film and the substrate do not substantially undergo alteration or decomposition due to the patterning of the organic film, an organic semiconductor device.

12. The patterned organic film includes 10 or more organic films, each organic film having a thickness of 2 nm or more, a width of 500 nm or more, and a length of 500 nm or more, and the distance between adjacent organic films being 1 μm or more. The organic semiconductor device according to claim 11.

13. The patterned organic film is 0.0001 mm ２ The organic semiconductor device according to claim 11 or 12, which is an organic semiconductor single crystal film having a single domain of 0.0001 mm or more.

14. The organic semiconductor device according to any one of claims 11 to 13, including electrodes on at least a part between the substrate and the organic film, at least a part on the side opposite to the substrate with respect to the organic film, or both of them.

15. The organic semiconductor device according to claim 14, including a space between the substrate, the organic film, and the electrode.

16. An integrated circuit including the organic semiconductor device according to any one of claims 11 to 15.

Images