Organic semiconductor device, method for producing organic semiconductor single crystal film, and method for producing organic semiconductor device

Abstract

The present invention provides an organic semiconductor single crystal film which can be arranged on a desired substrate and has a thinner film thickness than before. The present invention relates to an organic semiconductor device, comprising a substrate and an organic semiconductor single crystal film on the substrate, wherein the average film thickness of the organic semiconductor single crystal film is 2 to 100 nm, and at least a portion of the surface of the substrate in contact with the organic semiconductor single crystal film is hydrophobic, solvent-soluble, non-heat-resistant, or a combination thereof with a contact angle of 80 degrees or more.

Description

Technical Field

[0001] The present invention relates to an organic semiconductor device, a method for producing an organic semiconductor single crystal film, and a method for producing an organic semiconductor device. Background Art

[0002] In recent years, attention has been paid to organic semiconductors. Unlike conventional inorganic semiconductors such as amorphous silicon and polycrystalline silicon, organic semiconductors have the following characteristics: excellent flexibility and the ability to be economically produced on a large surface area through a roll-to-roll process. Research is underway into the application of organic semiconductors as pillar silicon semiconductors in next-generation electronic devices.

[0003] In particular, it is known that an organic semiconductor device with excellent characteristics can be produced by forming an organic semiconductor single crystal film on a hydrophobic substrate such as a fluorine-based polymer insulating film.

[0004] In addition, as a method for manufacturing organic semiconductor devices, film formation methods such as coating methods and vapor phase growth methods (PVT: Physical Vapor Transport) have been used in the past (Patent Document 1, Non-Patent Document 1). In particular, by using the coating method as a film formation method, it is expected that the material utilization efficiency will be improved and the cost will be greatly reduced.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2015-185620

[0008] Non-patent literature

[0009] Non-patent literature 1: Balthasar Blulle, et al., Approaching the trap-free limitin organic single-crystal field-effect transistors, Physical Review Applied 1,034006(2014)

[0010] Non-patent literature 2: M.Kitamura et al., Work function of gold surfaces modified using substituted benzenethiols: Reaction time dependence and thermalstability, Appl.Phys.Express 7,035701(2014) Summary of the invention

[0011] Problems to be solved by the invention

[0012] However, conventionally, when the vapor phase growth method is used, only an organic semiconductor single crystal film having a thickness of about 2 μm can be obtained, and it is difficult to obtain an organic semiconductor single crystal film having a thickness thinner than 2 μm.

[0013] Furthermore, when a coating method is used, an organic semiconductor film cannot be formed on a hydrophobic substrate such as a fluorine-based polymer insulating film.

[0014] In addition, since an organic solvent is used in the coating method, an organic semiconductor film cannot be coated on a substrate that is soluble in the solvent. Therefore, for example, it is difficult to form a pn junction structure composed of an organic semiconductor film by the coating method.

[0015] In addition, when there is an electrode film such as Au on the substrate, in order to control the work function of the electrode and improve the carrier injection from the electrode to the organic semiconductor, although the surface of the electrode film is modified by a self-assembled monolayer (SAM: Self-Assembled Monolayer) such as pentafluorobenzenethiol (PFBT) or 4-methylbenzenethiol (MBT), the heat resistance of the PFBT film or the MBT film is low, and the work function control effect of PFBT decreases at about 130 to 150°C, and the work function control effect of MBT decreases at about 100°C (Non-Patent Document 2). The coating method is mostly carried out by heating the substrate to about 80 to 150°C, so it is sometimes inappropriate to form an organic semiconductor on a substrate having an electrode film such as Au by a coating method.

[0016] Thus, when the vapor phase growth method is used, a thin organic semiconductor single crystal film cannot be obtained, and when the coating method is used, there are limitations on the substrate.

[0017] Therefore, there is a need for an organic semiconductor single crystal film that can be arranged on a desired substrate and has a thinner film thickness than conventional ones.

[0018] Technical solutions to solve problems

[0019] (1) An organic semiconductor device comprising:

[0020] Substrate, and

[0021] The organic semiconductor single crystal film on the substrate,

[0022] The average film thickness of the organic semiconductor single crystal film is 2 to 100 nm.

[0023] At least a portion of a surface of the substrate in contact with the organic semiconductor single crystal film is hydrophobic, solvent-soluble, non-heat-resistant, or a combination thereof.

[0024] (2) The organic semiconductor device according to (1) above, wherein the area of ​​the organic semiconductor single crystal film is 2 mm 2 above.

[0025] (3) A method for manufacturing an organic semiconductor single crystal film, comprising:

[0026] A step of forming an organic semiconductor single crystal film having an average film thickness of 2 to 100 nm on a hydrophilic and water-insoluble first substrate by a coating method; and

[0027] a step of applying water to an interface between the first substrate and the organic semiconductor single crystal film to separate the organic semiconductor single crystal film from the first substrate.

[0028] (4) The method for producing an organic semiconductor single crystal film according to (3) above, wherein the area of ​​the organic semiconductor single crystal film is 2 mm 2 above.

[0029] (5) A method for manufacturing an organic semiconductor single crystal film according to (3) or (4) above, wherein the contact angle of the first substrate is smaller than the contact angle of the organic semiconductor single crystal film, and the difference between the contact angles of the first substrate and the organic semiconductor single crystal film is greater than 80 degrees.

[0030] (6) A method for manufacturing an organic semiconductor single crystal film according to any one of (3) to (5) above, wherein the step of applying water to the interface between the first substrate and the organic semiconductor single crystal film includes the step of immersing the first substrate on which the organic semiconductor single crystal film is formed in water.

[0031] (7) A method for producing an organic semiconductor device, comprising the step of disposing the organic semiconductor single crystal film produced by the method for producing an organic semiconductor single crystal film according to any one of (3) to (6) above on a second substrate,

[0032] At least a portion of a surface of the second substrate in contact with the organic semiconductor single crystal film is hydrophobic, solvent-soluble, non-heat-resistant, or a combination thereof.

[0033] (8) A method for manufacturing an organic semiconductor device according to (7) above, wherein the step of configuring the organic semiconductor single crystal film on a second substrate includes the following steps: configuring the second substrate so that it is in contact with the organic semiconductor single crystal film formed on the first substrate, and applying water to the interface between the first substrate and the organic semiconductor single crystal film to separate the organic semiconductor single crystal film from the first substrate and configure it on the second substrate.

[0034] (9) A method for manufacturing an organic semiconductor device according to (7) or (8) above, wherein at least a portion of a surface of the second substrate in contact with the organic semiconductor single crystal film has at least one of a concave portion, a convex portion, a concave-convex portion, and an electrode.

[0035] Effects of the Invention

[0036] According to the present invention, it is possible to obtain an organic semiconductor single crystal film having a thinner film thickness than conventional ones, which can be arranged on a desired substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a schematic cross-sectional view of an organic semiconductor single crystal film formed on a mica substrate.

[0038] Figure 2 This is a schematic diagram showing a state in which a hydrophilic substrate on which an organic semiconductor single crystal film is formed is immersed in water and the organic semiconductor single crystal film floats on the water surface.

[0039] Figure 3 This is an electron diffraction pattern obtained by observing the obtained organic semiconductor single crystal film with a transmission electron microscope (TEM).

[0040] Figure 4 This is a schematic diagram showing a state where an organic semiconductor single crystal film transferred onto a mica substrate is formed on a CYTOP (registered trademark) / SiO2 / Si substrate.

[0041] Figure 5 This is a polarization microscope image obtained by observing the surface of an organic semiconductor single crystal film disposed on CYTOP (registered trademark).

[0042] Figure 6 It is a schematic cross-sectional view of an organic semiconductor single crystal film and an Au electrode arranged on a CYTOP (registered trademark) / SiO2 / Si substrate.

[0043] Figure 7 This is a polarized light microscope image obtained by observing the upper surface of the fabricated BGTC-type OFET.

[0044] Figure 8 It is a graph of transfer characteristics showing the relationship between the gate voltage and the drain current in the saturation region.

[0045] Fig. 9 It is a graph showing the transfer characteristics of the relationship between the gate voltage and the drain current in the linear region.

[0046] Fig.10 This is a graph showing output characteristics of the relationship between the drain voltage and the drain current due to the gate voltage.

[0047] Fig.11It is a schematic diagram showing the state of an organic semiconductor single crystal film transferred onto a mica substrate and formed on a polyparaxylene / SiO2 / Si substrate.

[0048] Fig.12 This is a polarization microscope image obtained by observing the surface of an organic semiconductor single crystal film disposed on polyparaxylene.

[0049] Fig.13 This is a schematic diagram showing a state where an organic semiconductor single crystal film formed by transfer on a mica substrate is formed on a PDMS / PET substrate having an Au electrode.

[0050] Fig.14 This is a polarization microscope image obtained by observing the surface of an organic semiconductor single crystal film arranged on Au and PDMS / PET substrates.

[0051] Fig.15 This is a schematic diagram showing a state where an organic semiconductor single crystal film transferred onto an EAGLE glass substrate is formed on a parylene / polyimide substrate having an Au electrode.

[0052] Fig.16 It is a schematic cross-sectional view of an organic semiconductor single crystal film disposed on a polyparaxylene (diX-SR (registered trademark)) / polyimide (PI) substrate having an Au electrode modified with PFBT.

[0053] Fig.17 It is a schematic cross-sectional view of a top-gate bottom-contact (TGBC) type organic field-effect transistor (OFET).

[0054] Fig.18 This is a polarized light microscope image obtained by observing the upper surface of the fabricated TGBC-type OFET.

[0055] Fig.19 This is a graph showing the relationship between the gate voltage and the drain current in the saturation region.

[0056] Fig. 20 This is a graph showing the relationship between the gate voltage and the drain current in the linear region.

[0057] Fig.21 This is a graph showing the relationship between the drain voltage and the drain current caused by the gate voltage.

[0058] Fig. 22 This is a schematic diagram showing a state where an organic semiconductor single crystal film transferred onto an EAGLE glass substrate is formed on a CYTOP (registered trademark) / SiO2 / Si substrate having an Au electrode modified by PFBT.

[0059] Fig.23It is a schematic cross-sectional view of an organic semiconductor single crystal film arranged on a CYTOP (registered trademark) / SiO2 / Si substrate having an Au electrode modified by PFBT.

[0060] Fig.24 It is a schematic cross-sectional view of a top-gate bottom-contact (TGBC) type organic field-effect transistor (OFET).

[0061] Fig.25 This is a polarized light microscope image obtained by observing the upper surface of the fabricated TGBC-type OFET.

[0062] Fig.26 This is a graph showing the relationship between the gate voltage and the drain current in the saturation region.

[0063] Fig. 27 This is a graph showing the relationship between the gate voltage and the drain current in the linear region.

[0064] Fig.28 This is a graph showing the relationship between the drain voltage and the drain current caused by the gate voltage.

[0065] Fig.29 This is a confocal laser microscope image of an organic semiconductor single crystal film transferred onto an EAGLE glass substrate and observed from the surface of an organic semiconductor single crystal film arranged on a CYTOP (registered trademark) / SiO2 / Si substrate.

[0066] Fig.30 This is the result obtained by single crystal X-ray diffraction experiment of the obtained organic semiconductor single crystal film. DETAILED DESCRIPTION

[0067] The present invention takes an organic semiconductor device as an object, which includes a substrate and an organic semiconductor single crystal film on the above-mentioned substrate, the average film thickness of the above-mentioned organic semiconductor single crystal film is 2 to 100 nm, and at least a portion of the surface of the above-mentioned substrate that is in contact with the above-mentioned organic semiconductor single crystal film is hydrophobic, solvent-soluble, non-heat-resistant or a combination thereof.

[0068] The average film thickness of the organic semiconductor single crystal film in the organic semiconductor device of the present invention is 2 to 100 nm, preferably 4 to 20 nm. By making the average film thickness of the organic semiconductor single crystal film within the above range, good device characteristics can be obtained. The average film thickness of the organic semiconductor single crystal film can be measured using a stylus-type surface shape measuring instrument or an atomic force microscope.

[0069] The organic semiconductor single crystal film of the organic semiconductor device of the present invention preferably has 1 to 50 molecular layers in the thickness direction, more preferably 1 to 10 molecular layers, and further preferably 1 to 5 molecular layers. The organic semiconductor single crystal film of the organic semiconductor device of the present invention most preferably has 1 molecular layer, but may also have two or more molecular layers in the thickness direction. The number of molecular layers of the organic semiconductor single crystal film can be measured by atomic force microscopy.

[0070] The thickness of one molecular layer of the organic semiconductor single crystal film of the organic semiconductor device of the present invention 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 microscopy observation.

[0071] The area of ​​the organic semiconductor single crystal film of the organic semiconductor device of the present invention is preferably 2 mm 2 More than 10 mm is more preferred 2 More than, more preferably 100mm 2 More preferably, 1000 mm 2 More preferably, 10000 mm 2 The upper limit of the area of ​​the organic semiconductor single crystal film is not particularly limited, and can be limited according to the size of the manufacturing equipment, for example, it can be set to 10m 2 In the past, when using the vapor phase growth method, only a maximum of 1 mm 2 In contrast to an organic semiconductor single crystal film having an area of ​​about 200 Å, the organic semiconductor device of the present invention can have a large area as described above.

[0072] The organic semiconductor single crystal film of the organic semiconductor device of the present invention is composed of a single domain or multiple domains, preferably a single domain. The domain of the organic semiconductor single crystal film can be determined by single crystal X-ray diffraction. The organic semiconductor single crystal film of the organic semiconductor device of the present invention has a thickness of preferably 0.005 mm. 2 More preferably 0.5 mm 2 More preferably, 2.0 mm 2 A single domain of continuous area above.

[0073] The organic semiconductor single crystal film of the organic semiconductor device of the present invention preferably has a thickness of 0.5 cm 2 / V·s or more, more preferably 3.0cm 2 / V·s or more, more preferably 5.0cm 2 / V·s or more, and more preferably 7.5cm 2 / V·s or more, more preferably 10cm 2The mobility of the organic semiconductor single crystal film can be calculated from the measurement results of the organic field effect transistor.

[0074] In the organic semiconductor device of the present invention, at least a portion of the surface of the substrate in contact with the organic semiconductor single crystal film has the characteristics of hydrophobicity, solvent solubility, non-heat resistance, or a combination thereof. Preferably, the entire surface of the substrate in contact with the organic semiconductor single crystal film has the characteristics of hydrophobicity, solvent solubility, non-heat resistance, or a combination thereof, and more preferably, the entire substrate has the characteristics of hydrophobicity, solvent solubility, non-heat resistance, or a combination thereof.

[0075] In the present invention, hydrophobicity means that the contact angle is preferably 80 degrees or more, more preferably 90 degrees or more, further preferably 100 degrees or more, further more preferably 110 degrees or more, further more preferably 150 degrees or more.

[0076] At least a portion of the surface of the substrate of the organic semiconductor device of the present invention that is in contact with the organic semiconductor single crystal film shows hydrophobicity within the above-mentioned preferred range, preferably the entire surface of the substrate that is in contact with the organic semiconductor single crystal film shows hydrophobicity within the above-mentioned preferred range, and more preferably the entire substrate shows hydrophobicity within the above-mentioned preferred range. Thus, when a device is manufactured using an organic semiconductor single crystal film configured on a hydrophobic substrate, moisture (adsorbed molecules) that can adhere to the substrate can be reduced or eliminated, and a device with good characteristics that is not affected by moisture can be manufactured.

[0077] Examples of the hydrophobic substrate include polyparaxylene (contact angle of about 80 to 90 degrees) and CYTOP (registered trademark) of a fluorine-based polymer (contact angle of 110 degrees).

[0078] In the present invention, solvent solubility means that the substance actually dissolves, decomposes or swells in an organic solvent, and for example, means that the substance actually dissolves, decomposes or swells in an organic solvent conventionally used in a coating method, such as toluene and dichlorobenzene.

[0079] At least a portion of the surface of the substrate of the organic semiconductor device of the present invention that is in contact with the organic semiconductor single crystal film may be solvent soluble, preferably the entire surface of the substrate that is in contact with the organic semiconductor single crystal film may be solvent soluble, and more preferably the entire substrate may be solvent soluble. Therefore, at least a portion of the surface of the substrate that is in contact with the organic semiconductor single crystal film, preferably the entire surface of the substrate that is in contact with the organic semiconductor single crystal film, and more preferably the entire substrate may be a p-type organic semiconductor film or an n-type organic semiconductor film, or may be a laminate comprising a p-type organic semiconductor film and an n-type organic semiconductor film. Therefore, the substrate of the electronic device of the present invention can include a pn junction structure, a pnp junction structure, or an npn junction structure based on an organic semiconductor film.

[0080] In the present invention, non-heat resistant means that the glass transition point is preferably 90°C or lower, or sublimates, melts or decomposes at 90°C or lower, and more preferably the glass transition point is 120°C or lower, or sublimates, melts or decomposes at 120°C or lower.

[0081] At least a portion of the surface of the substrate of the organic semiconductor device of the present invention that is in contact with the organic semiconductor single crystal film, preferably the entire surface of the substrate that is in contact with the organic semiconductor single crystal film, and more preferably the entire substrate can be non-heat-resistant. Therefore, at least a portion of the surface of the substrate that is in contact with the organic semiconductor single crystal film, preferably the entire surface of the substrate that is in contact with the organic semiconductor single crystal film, and more preferably the entire substrate can be, for example, a substrate having an electrode film such as Au modified with a self-assembled monolayer (SAM: self-assembled monolayer) such as pentafluorobenzenethiol (PFBT). An organic semiconductor single crystal film can be arranged on the above-mentioned PFBT or other low-heat-resistant modifying material.

[0082] The type of organic semiconductor constituting the organic semiconductor single crystal film of the organic semiconductor device of the present invention is not particularly limited. For example, polycyclic aromatic compounds with four or more rings, one or more unsaturated five-membered heterocyclic compounds, and polycyclic compounds with four or more rings derived from multiple benzene rings can be used.

[0083] The organic semiconductor constituting the organic semiconductor single crystal film of the organic semiconductor device of the present invention is preferably a material with high self-condensation function, and examples thereof include p-type organic semiconductor Cn-DNBDT-NW of the following chemical formula (1) which exhibits high mobility.

[0084] [Chemical formula 1]

[0085]

[0086] In formula (1), n ​​may be 1 to 14. The self-condensation function refers to the tendency of molecules to spontaneously condense and easily crystallize when they are precipitated from a solvent.

[0087] Other examples of the organic semiconductor constituting the organic semiconductor single crystal film of the organic semiconductor device of the present invention are shown in the following chemical formulas (2) to (6).

[0088] [Chemical formula 2]

[0089]

[0090] 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 heteroatom (typically selected from an oxygen atom and a sulfur atom). In addition, R1 and R2 can also form a ring together. For reasons of self-cohesion performance, it is preferred that R1 and R2 are each independently a hydrogen atom or an alkyl group having 5 to 8 carbon atoms. It is more preferred that R1 and R2 are each independently a hydrogen atom or a hexyl group.

[0091] n represents an integer of 5 to 100. n represents 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.

[0092] [Chemical formula 3]

[0093]

[0094] 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 the hydrogen atom in the alkyl group may be substituted by a substituent such as a halogen atom. For the sake of self-condensation performance, R4=R5 is preferred, and R3=R6 is preferred. From the viewpoint of solubility, it is preferred that R4 and R5 are hydrogen atoms, R3 and R6 are each independently an alkyl group having 1 to 14 carbon atoms, or R3 and R6 are hydrogen atoms, R4 and R5 are each independently an alkyl group having 1 to 14 carbon atoms. It is more preferred that R3 and R6 are hydrogen atoms, and R4 and R5 are each independently an alkyl group having 1 to 14 carbon atoms. For the sake of self-condensation performance, the preferred number of carbon atoms in the alkyl group is 4 to 12, and more preferably 6 to 10.

[0095] [Chemical formula 4]

[0096]

[0097] 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 the hydrogen atom in the alkyl group may be substituted by a substituent such as a halogen atom. For the sake of self-condensation performance, R7=R9 is preferred, and R8=R10 is preferred. From the viewpoint of solubility, it is preferred that R7 and R9 are hydrogen atoms, and R8 and R10 are each independently an alkyl group having 1 to 14 carbon atoms, or that R8 and R10 are hydrogen atoms, and R7 and R9 are each independently an alkyl group having 1 to 14 carbon atoms. It is more preferred that R8 and R10 are hydrogen atoms, and R7 and R9 are each independently an alkyl group having 1 to 14 carbon atoms. For the sake of self-condensation performance, the preferred number of carbon atoms in the alkyl group is 6 to 13, and more preferably 8 to 10.

[0098] [Chemical formula 5]

[0099]

[0100] 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 the hydrogen atom in the alkyl group may be substituted by a substituent such as a halogen atom. For the sake of self-condensation performance, preferably R11=R13, and preferably R12=R14. From the viewpoint of solubility, it is preferred that R11 and R13 are hydrogen atoms, and R12 and R14 are each independently an alkyl group having 1 to 14 carbon atoms, or that R12 and R14 are hydrogen atoms, and R11 and R13 are each independently an alkyl group having 1 to 14 carbon atoms. It is more preferred that R12 and R14 are hydrogen atoms, and R11 and R13 are each independently an alkyl group having 1 to 14 carbon atoms. For the sake of self-condensation performance, the preferred carbon number of the alkyl group is 5 to 12, and more preferably 8 to 10.

[0101] [Chemical formula 6]

[0102]

[0103] 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 an oxygen atom and a sulfur atom), and the hydrogen atom in the alkyl group may be substituted by a substituent such as a halogen atom. For the sake of self-condensation performance, R15=R17 is preferred, and R16=R18 is preferred. From the viewpoint of solubility, it is preferred that R16 and R18 are hydrogen atoms, and R15 and R17 are each independently an alkyl group having 1 to 14 carbon atoms, or that R15 and R17 are hydrogen atoms, and R16 and R18 are each independently an alkyl group having 1 to 14 carbon atoms. It is more preferred that R16 and R18 are hydrogen atoms, and R15 and R17 are each independently an alkyl group having 1 to 14 carbon atoms. For the sake of self-condensation performance, the preferred carbon number of the alkyl group is 5 to 12, and more preferably 8 to 10.

[0104] Another example of an organic semiconductor constituting the organic semiconductor single crystal film of the organic semiconductor device of the present invention is shown in the following chemical formulas (7) to (15). In chemical formulas (7) to (15), R can be a linear alkyl group, a branched alkyl group, a fluorinated linear / branched alkyl group, a triisopropylsilylethynyl group, a phenyl group, or the like.

[0105] [Chemical formula 7]

[0106]

[0107] [Chemical formula 8]

[0108]

[0109] [Chemical formula 9]

[0110]

[0111] [Chemical formula 10]

[0112]

[0113] [Chemical formula 11]

[0114]

[0115] [Chemical formula 12]

[0116]

[0117] [Chemical formula 13]

[0118]

[0119] [Chemical formula 14]

[0120]

[0121] [Chemical formula 15]

[0122]

[0123] Whether or not the organic semiconductor single crystal film is a single crystal can be confirmed by observation using a transmission electron microscope (TEM).

[0124] The organic semiconductor device of the present invention may 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, or the like.

[0125] The present invention also takes a method for manufacturing an organic semiconductor single crystal film as an object, and the method for manufacturing an organic semiconductor single crystal film includes: a process of forming an organic semiconductor single crystal film with an average film thickness of 2 to 100 nm on a hydrophilic and water-insoluble first substrate using a coating method; and a process of applying water to the interface between the first substrate and the organic semiconductor single crystal film to separate the organic semiconductor single crystal film from the first substrate.

[0126] According to the method for producing an organic semiconductor single crystal film of the present invention, it is possible to provide an organic semiconductor single crystal film which can be arranged on a desired substrate and has a thinner film thickness than conventional films.

[0127] In the method for producing an organic semiconductor single crystal film of the present invention, a coating method is used to form an organic semiconductor single crystal film with an average film thickness of 2 to 100 nm on a hydrophilic and water-insoluble first substrate. The coating method is a method in which an organic semiconductor is dissolved in an organic solvent to prepare an organic semiconductor solution, the organic semiconductor solution is coated on a substrate, and the organic solvent is evaporated to form a film. As the organic solvent, an organic solvent conventionally used in the coating method can be used, for example, toluene, dichlorobenzene, etc. can be used.

[0128] In the method for manufacturing the organic semiconductor single crystal film of the present invention, as a coating method, a conventional method can be used, for example: edge casting, continuous edge casting, drop casting, spin coating, printing (inkjet method, gravure printing method), disperser method, as well as spraying method, dip coating method, slit coater method, roll coater method, rod coater method, blade coating method, etc.

[0129] The first substrate is a hydrophilic substrate with a contact angle of water preferably below 20 degrees, more preferably below 10 degrees. The first substrate is water-insoluble, and may be, for example, mica or glass. The first substrate is water-insoluble, and therefore, when water is applied to the interface between the first substrate and the organic semiconductor single crystal film, the components of the first substrate are dissolved without being attached to the organic semiconductor single crystal film or reacting, and a high-purity organic semiconductor single crystal film can be obtained. In addition, when water is applied to the interface between the first substrate and the organic semiconductor single crystal film, in order to maintain the shape of the first substrate without destroying it, the shape of the organic semiconductor single crystal film can be separated from the first substrate without straining it. Water-insoluble means that it does not substantially dissolve, decompose or swell in water. The glass is preferably glass obtained by treating the surface with hydrophilization by UV ozone treatment or a hydrophilic coating material.

[0130] Water is applied to the interface between the first substrate and the organic semiconductor single crystal film to separate the organic semiconductor single crystal film from the first substrate. The molecules of the organic semiconductor single crystal film coated on the first substrate are hydrophobic, so water enters between the hydrophilic first substrate and the molecules of the hydrophobic organic semiconductor single crystal film, and the organic semiconductor single crystal film can be separated from the first substrate.

[0131] The contact angle of water of the hydrophilic first substrate is smaller than the contact angle of water of the hydrophobic organic semiconductor single crystal film, and the difference between the contact angles of water of the first substrate and the organic semiconductor single crystal film is preferably 80 degrees or more, more preferably 90 degrees or more. The contact angle of the organic semiconductor single crystal film is preferably 100 to 120 degrees. By making the difference in the contact angles of the hydrophilic first substrate and the hydrophobic organic semiconductor single crystal film within the above preferred range, the organic semiconductor single crystal film can be more stably peeled off from the first substrate.

[0132] The method of applying water to the interface between the first substrate and the organic semiconductor single crystal film is not particularly limited, and may be a method such as immersing the first substrate having the organic semiconductor single crystal film formed thereon in water and dripping water to the interface between the first substrate and the organic semiconductor single crystal film using a water pipette.

[0133] The method of applying water at the interface between the first substrate and the organic semiconductor single crystal film preferably comprises immersing the first substrate on which the organic semiconductor single crystal film is formed in water. By immersing the first substrate on which the organic semiconductor single crystal film is formed in water, the organic semiconductor single crystal film is separated from the first substrate in water, and a self-standing organic semiconductor single crystal film in water can be obtained. The self-standing organic semiconductor single crystal film can be arranged on any substrate such as a hydrophobic substrate, a solvent-soluble substrate, a non-heat-resistant substrate, or a substrate having a concave portion, a convex portion, a concave-convex portion or an electrode, a mesh-shaped or net-shaped substrate of the above-mentioned organic semiconductor device.

[0134] The average film thickness, molecular layer, area, domain, and mobility of the organic semiconductor single crystal film obtained by the method for producing an organic semiconductor single crystal film of the present invention can be applied to the contents related to the organic semiconductor single crystal film of the above-mentioned organic semiconductor device.

[0135] The present invention also takes a method for manufacturing an organic semiconductor device as an object, which method for manufacturing an organic semiconductor device includes a step of configuring an organic semiconductor single crystal film manufactured by the method for manufacturing an organic semiconductor single crystal film described above on a second substrate, wherein at least a portion of the surface of the second substrate in contact with the organic semiconductor single crystal film is hydrophobic, solvent-soluble, non-heat-resistant, or a combination thereof.

[0136] In the method for manufacturing an organic semiconductor device of the present invention, the organic semiconductor single crystal film separated from the first substrate by the method for manufacturing an organic semiconductor single crystal film described above is disposed on the second substrate.

[0137] At least a portion of the surface of the second substrate on which the organic semiconductor single crystal film is disposed, which is in contact with the organic semiconductor single crystal film, has the characteristics of hydrophobicity, solvent solubility, non-heat resistance, or a combination thereof. Preferably, the entire surface of the second substrate in contact with the organic semiconductor single crystal film has the characteristics of hydrophobicity, solvent solubility, non-heat resistance, or a combination thereof, and more preferably, the entire second substrate has the characteristics of hydrophobicity, solvent solubility, non-heat resistance, or a combination thereof.

[0138] The contents related to the hydrophobicity, solvent solubility, and non-heat resistance of the second substrate can be applied to the contents described with respect to the hydrophobicity, solvent solubility, and non-heat resistance of the substrate of the above-mentioned organic semiconductor device.

[0139] The step of disposing the organic semiconductor single crystal film on the second substrate preferably includes the following steps: disposing the second substrate so as to be in contact with the organic semiconductor single crystal film formed on the first substrate, and applying water to the interface between the first substrate and the organic semiconductor single crystal film to separate the organic semiconductor single crystal film from the first substrate and dispose it on the second substrate. In this way, by disposing the second substrate so as to be in contact with the organic semiconductor single crystal film and separating the organic semiconductor single crystal film from the first substrate, the organic semiconductor single crystal film can be directly transferred from the first substrate to the second substrate.

[0140] In another method, the step of disposing the organic semiconductor single crystal film on the second substrate preferably includes the following steps: immersing the first substrate on which the organic semiconductor single crystal film is formed in water, separating the organic semiconductor single crystal film from the first substrate in water to obtain a self-standing organic semiconductor single crystal film, and disposing the organic semiconductor single crystal film on the second substrate in water. In this way, by disposing the self-standing organic semiconductor single crystal film on the second substrate in water, the organic semiconductor single crystal film can be easily transferred from the first substrate to the second substrate.

[0141] It is further preferred that the step of disposing the organic semiconductor single crystal film on the second substrate includes the following step: disposing the second substrate so as to be in contact with the organic semiconductor single crystal film formed on the first substrate, and immersing the first substrate, the organic semiconductor single crystal film, and the second substrate in water to transfer the organic semiconductor single crystal film from the first substrate to the second substrate. In this way, by disposing the second substrate in water so as to be in contact with the organic semiconductor single crystal film and separating the organic semiconductor single crystal film from the first substrate, the organic semiconductor single crystal film can be more easily transferred from the first substrate to the second substrate.

[0142] The second substrate may have at least one of a concave portion, a convex portion, a concavo-convex portion, and an electrode in at least a portion of the surface of the second substrate in contact with the organic semiconductor single crystal film.

[0143] In the past, when using a coating method to make a top-gate structure transistor, it was necessary to coat an organic semiconductor on a substrate with an electrode. However, due to the surface energy difference between the electrode and the substrate and the height difference between the convex part of the electrode and the concave part of the substrate, the crystallinity and thickness of the organic semiconductor could not be uniformly formed, making it difficult to obtain good transistor characteristics.

[0144] According to the method for producing an organic semiconductor of the present invention, even if the second substrate has an electrode, the organic semiconductor single crystal film peeled from the first substrate is brought into contact with the second substrate, thereby allowing the organic semiconductor single crystal film to be arranged with a uniform thickness on the second substrate having the electrode.

[0145] The second substrate may also have a concave portion, a convex portion, or a concavo-convex portion caused by or not caused by an electrode. The concave portion, the convex portion, or the concavo-convex portion may be a rectangular shape, a curved shape, or a combination thereof. The depth of the concave portion, the height of the convex portion, and the depth of the concavo-convex portion (the distance in the thickness direction of the substrate between the lowest part of the concave portion and the last part of the convex portion) on the second substrate are each preferably more than 0 nm and less than 30 nm.

[0146] Example

[0147] (Example 1)

[0148] A natural mica substrate was prepared as a hydrophilic substrate, and the following chemical formula (16) showing high mobility was prepared as an organic semiconductor:

[0149] [Chemical formula 16]

[0150]

[0151] The p-type organic semiconductor C9-DNBDT-NW powder was prepared. 3-Chlorothiophene was used as a solvent to dissolve the organic semiconductor powder in the solvent to prepare an organic semiconductor solution. The prepared organic semiconductor solution was applied to a mica substrate heated to 100°C by a continuous edge casting method to prepare Figure 1 The average thickness is 12nm and the area is 200mm 2 Organic semiconductor single crystal film. The contact angle of water on the surface of the organic semiconductor single crystal film is 108 degrees. Figure 1 Schematic diagram of the cross section of an organic semiconductor single crystal film prepared on a mica substrate.

[0152] like Figure 2 As shown, a hydrophilic substrate on which an organic semiconductor single crystal film is formed is immersed in water, and the organic semiconductor single crystal film is peeled off from the hydrophilic substrate. The organic semiconductor single crystal film is in a free standing state on the water surface. Being free standing on the water surface means that the organic semiconductor single crystal film floats on the water surface while maintaining the crystalline structure without a supporting substrate. Figure 2 This is a schematic diagram showing a state where a hydrophilic substrate having an organic semiconductor single crystal film formed thereon is immersed in water.

[0153] Figure 3 The electron diffraction pattern of the obtained organic semiconductor single crystal film observed by transmission electron microscopy (TEM) is shown. Even after being peeled off from the hydrophilic substrate, it was confirmed that the organic semiconductor single crystal film maintained single crystallinity.

[0154] (Example 2)

[0155] Similar to Example 1, an organic semiconductor single crystal film of a p-type organic semiconductor C9-DNBDT-NW of the chemical formula (16) was prepared on a mica substrate.

[0156] As a hydrophobic substrate, a CYTOP (registered trademark) / SiO 2 / Si substrate prepared with CYTOP (registered trademark)-809M was prepared.

[0157] like Figure 4 As shown, a CYTOP (registered trademark) / SiO2 / Si substrate is configured so that the CYTOP (registered trademark) is in contact with an organic semiconductor single crystal film formed on a mica substrate, and water is dripped at the interface between the mica substrate and the organic semiconductor single crystal film to peel off the organic semiconductor single crystal film from the mica substrate and transfer it to the CYTOP (registered trademark). Figure 4 This is a schematic diagram showing a state where an organic semiconductor single crystal film formed on a mica substrate is transferred onto a CYTOP (registered trademark) / SiO2 / Si substrate. Figure 5 The figure shows a polarization microscope image of an organic semiconductor single crystal film disposed on CYTOP (registered trademark) observed from the surface.

[0158] like Figure 6 As shown, on an organic semiconductor single crystal film of C9-DNBDT-NW configured on a CYTOP (registered trademark) / SiO2 / Si substrate, a 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 using a metal mask as an S / D electrode (source / drain electrode) to produce a bottom gate top contact (BGTC) type organic field effect transistor (OFET). Figure 6 It is a schematic cross-sectional view of an organic semiconductor single crystal film and an Au electrode arranged on a CYTOP (registered trademark) / SiO2 / Si substrate. Figure 7 The figure shows a polarization microscope image obtained by observing the upper surface of the fabricated BGTC-type OFET.

[0159] Figure 8 is a graph showing the transfer characteristics of the relationship between the gate voltage and the drain current in the saturation region. Fig. 9 is a graph showing the transfer characteristics of the relationship between the gate voltage and the drain current in the linear region. Fig.10 A graph showing the output characteristics of the relationship between the drain voltage and drain current due to the gate voltage. The mobility in the saturation region is 13 cm 2 / V·s, the mobility in the linear region shows 10cm 2 / V·s, showing a very large mobility.

[0160] (Example 3)

[0161] Similar to Example 1, an organic semiconductor single crystal film of a p-type organic semiconductor C9-DNBDT-NW of formula (16) was formed on a mica substrate.

[0162] As a hydrophobic substrate, a polyparaxylene / SiO 2 / Si substrate prepared with polyparaxylene (diX-SR (registered trademark)) was prepared.

[0163] like Fig.11 As shown, a polyparaxylene / SiO2 / Si substrate is configured so that the polyparaxylene is in contact with the organic semiconductor single crystal film formed on the mica substrate, and water is dripped on the interface between the mica substrate and the organic semiconductor single crystal film to peel off the organic semiconductor single crystal film from the mica substrate and transfer it to the polyparaxylene. Fig.11 This is a schematic diagram showing a state where an organic semiconductor single crystal film formed on a mica substrate is transferred to a polyparaxylene / SiO2 / Si substrate. Fig.12 FIG. 4 shows a polarization microscope image obtained by observing the surface of an organic semiconductor single crystal film disposed on polyparaxylene.

[0164] (Example 4)

[0165] Similar to Example 1, an organic semiconductor single crystal film of a p-type organic semiconductor C9-DNBDT-NW of the chemical formula (16) was prepared on a mica substrate.

[0166] As solvent soluble substrates, e.g. Fig.13 As shown, a polydimethylsiloxane (PDMS) / polyethylene terephthalate (PET) substrate was prepared on which Au electrodes of 0.5 mm in length, 0.5 mm in width, and 30 nm in height were formed as S / D electrodes (source / drain electrodes) by vacuum evaporation using a metal mask. Fig.13 This is a schematic diagram showing a state where an organic semiconductor single crystal film formed on a mica substrate is transferred onto a PDMS / PET substrate having an Au electrode.

[0167] like Fig.14 As shown, a PDMS / PET substrate with Au vacuum-evaporated thereon is configured so that the Au serving as the source / drain (S / D) electrode is in contact with the organic semiconductor single crystal film formed on the mica substrate, and water is dripped at the interface between the mica substrate and the organic semiconductor single crystal film to peel off the organic semiconductor single crystal film from the mica substrate and transfer it to the Au and PDMS / PET substrates. Fig.14 The polarization microscope image of the organic semiconductor single crystal film arranged on the Au and PDMS / PET substrates is shown as the surface is observed.

[0168] (Example 5)

[0169] An organic semiconductor single crystal film of p-type organic semiconductor C9-DNBDT-NW of chemical formula (16) was prepared in the same manner as in Example 1, except that EAGLE glass (manufactured by Corning) treated with UV / ozone was used as the hydrophilic substrate instead of the mica substrate.

[0170] As hydrophobic substrates, e.g. Fig.15 As shown, a polyparaxylene (diX-SR (registered trademark)) / polyimide (PI) substrate having the following Au electrodes is prepared, and Au electrodes with a length of 0.4 mm, a width of 2 mm, and a height of 12 nm are formed by vacuum evaporation using a metal mask as S / D electrodes (source / drain electrodes), and the Au electrodes are modified with a self-assembled monolayer of pentafluorobenzenethiol (PFBT). Fig.15 A schematic diagram showing a state in which an organic semiconductor single crystal film formed on an EAGLE glass substrate is transferred onto a polyparaxylene / polyimide substrate having an Au electrode.

[0171] A polyparaxylene (diX-SR (registered trademark)) / polyimide (PI) substrate having an Au electrode (S / D electrode) modified by PFBT is arranged, and the Au electrode (S / D electrode) modified by PFBT is brought into contact with an organic semiconductor single crystal film formed on an EAGLE glass substrate, and water is dripped at the interface between the EAGLE glass substrate and the organic semiconductor single crystal film to peel off the organic semiconductor single crystal film from the EAGLE glass substrate, as shown in FIG. Fig.16 As shown, the organic semiconductor single crystal film is transferred onto the Au electrode modified with PFBT and the polyparaxylene substrate. Fig.16 It is a schematic cross-sectional view of an organic semiconductor single crystal film disposed on a polyparaxylene (diX-SR (registered trademark)) / polyimide (PI) substrate having an Au electrode modified with PFBT.

[0172] In addition, if Fig.17 As shown, CYTOP (registered trademark), polyparaxylene (diX-SR (registered trademark)) and a gate electrode are formed on the C9-DNBDT-NW of the organic semiconductor single crystal film to produce a top gate bottom contact (TGBC) type organic field effect transistor (OFET). Fig.17 It is a schematic cross-sectional view of a TGBC-type OFET. Fig.18 The figure shows a polarization microscope image obtained by observing the upper surface of the fabricated TGBC-type OFET.

[0173] Fig.19 is a graph showing the transfer characteristics of the relationship between the gate voltage and the drain current in the saturation region. Fig. 20 is a graph showing the transfer characteristics of the relationship between the gate voltage and the drain current in the linear region. Fig.21A graph showing the output characteristics of the relationship between the drain voltage and drain current due to the gate voltage. The mobility in the saturation region is 3.2 cm 2 / V·s, the mobility in the linear region shows 4.1cm 2 / V·s, showing small hysteresis and large mobility.

[0174] (Example 6)

[0175] An organic semiconductor single crystal film of p-type organic semiconductor C9-DNBDT-NW of chemical formula (16) was prepared in the same manner as in Example 1, except that EAGLE glass (manufactured by Corning) treated with UV / ozone was used as the hydrophilic substrate instead of the mica substrate.

[0176] As hydrophobic substrates, e.g. Fig. 22 As shown, a CYTOP (registered trademark) / SiO2 / Si substrate having the following Au electrode is prepared, and an Au electrode with a length of 0.4 mm, a width of 2 mm and a height of 20 nm is formed by vacuum evaporation using a metal mask as an S / D electrode (source / drain electrode), and the Au electrode is modified using a self-assembled monolayer of pentafluorobenzenethiol (PFBT). Fig. 22 This is a schematic diagram showing a state where an organic semiconductor single crystal film formed on an EAGLE glass substrate is transferred onto a CYTOP (registered trademark) / SiO2 / Si substrate having an Au electrode modified with PFBT.

[0177] An EAGLE glass substrate having an Au electrode (S / D electrode) modified by PFBT is provided, and the Au electrode (S / D electrode) modified by PFBT is brought into contact with an organic semiconductor single crystal film formed on an EAGLE glass substrate, and water is dripped at the interface between the EAGLE glass substrate and the organic semiconductor single crystal film to peel off the organic semiconductor single crystal film from the EAGLE glass substrate. Fig.23 As shown, an organic semiconductor single crystal film was transferred onto an Au electrode modified with PFBT and a CYTOP (registered trademark) substrate. Fig.23 It is a schematic cross-sectional view of an organic semiconductor single crystal film disposed on a CYTOP (registered trademark) / SiO2 / Si substrate having an Au electrode modified with PFBT.

[0178] In addition, if Fig.24 As shown, CYTOP (registered trademark), polyparaxylene (diX-SR (registered trademark)) and a gate electrode are formed on the C9-DNBDT-NW of the organic semiconductor single crystal film to produce a top gate bottom contact (TGBC) type organic field effect transistor (OFET). Fig.24 It is a schematic cross-sectional view of a TGBC-type OFET. Fig.25The figure shows a polarization microscope image obtained by observing the upper surface of the fabricated TGBC-type OFET.

[0179] Fig.26 is a graph showing the transfer characteristics of the relationship between the gate voltage and the drain current in the saturation region. Fig. 27 is a graph showing the transfer characteristics of the relationship between the gate voltage and the drain current in the linear region. Fig.28 A graph showing the output characteristics of the relationship between the drain voltage and drain current due to the gate voltage. The mobility in the saturation region is 0.9 cm 2 / V·s, the mobility in the linear region shows 1.9cm 2 / V·s, showing small hysteresis and steep sub-threshold characteristics.

[0180] (Example 7)

[0181] An organic semiconductor single crystal film of p-type organic semiconductor C9-DNBDT-NW of chemical formula (16) was prepared in the same manner as in Example 1, except that EAGLE glass (manufactured by Corning) treated with UV / ozone was used as the hydrophilic substrate instead of the mica substrate.

[0182] As a hydrophobic substrate, a CYTOP (registered trademark) / SiO 2 / Si substrate prepared with CYTOP (registered trademark)-809M was prepared.

[0183] A CYTOP (registered trademark) / SiO2 / Si substrate was configured, and the CYTOP (registered trademark) was brought into contact with the organic semiconductor single crystal film formed on the EAGLE glass subjected to UV·ozone treatment, and water was dripped at the interface between the EAGLE glass and the organic semiconductor single crystal film to form a 1.7 cm 2 The organic semiconductor single crystal film was peeled off from the EAGLE glass substrate and transferred to CYTOP (registered trademark).

[0184] Fig.29 The confocal laser microscope image obtained by observing the surface of an organic semiconductor single crystal film arranged on a CYTOP (registered trademark) / SiO2 / Si substrate from an EAGLE glass substrate. The obtained organic semiconductor single crystal film has a 20 mm 2 A single domain of continuous area.

[0185] Twenty-four organic field effect transistors were fabricated using the obtained organic semiconductor single crystal film, and the mobility in the saturation region and the mobility in the linear region were measured. As a result, the average mobility in the saturation region was 10.8±1.8 cm 2 / V·s, and the average mobility in the linear region is 9.9±2.1cm 2 / V·s.

[0186] (Example 8)

[0187] An organic semiconductor single crystal film of p-type organic semiconductor C9-DNBDT-NW of chemical formula (16) was prepared in the same manner as in Example 1, except that EAGLE glass (manufactured by Corning) treated with UV / ozone was used as the hydrophilic substrate instead of the mica substrate.

[0188] A glass substrate with a thickness of 30 μm was prepared for single crystal X-ray diffraction measurement. The prepared glass substrate was arranged so as to contact the organic semiconductor single crystal film formed on the EAGLE glass obtained by UV·ozone treatment, and water was dripped at the interface between the organic semiconductor single crystal film and the glass substrate to peel the organic semiconductor single crystal film from the EAGLE glass substrate and transfer it to the glass substrate.

[0189] Fig.30 The single crystal X-ray diffraction measurement results of the organic semiconductor single crystal film transferred onto the glass substrate are shown. * The area surrounded by white circles corresponds to the crystal growth direction and represents the diffraction peak from the organic semiconductor single crystal film. It can be seen that a single point can be obtained by single crystal X-ray diffraction. The obtained organic semiconductor single crystal film is 0.00795 mm away from the X-ray irradiation. 2 The range is composed of a single domain.

Claims

1. An organic semiconductor device, It is characterized in that Include: Substrate, and The organic semiconductor single crystal film on the substrate, The organic semiconductor constituting the organic semiconductor single crystal film is a compound represented by the following formula (3), formula (4), formula (5) or formula (6): In formula (3), R 3 , R 4 , R 5 and R 6 are each independently: a hydrogen atom; or an alkyl group having 1 to 14 carbon atoms which may contain a heteroatom selected from an oxygen atom and a sulfur atom and may be substituted by a halogen atom, In formula (4), R 7 , R 8 , R 9 and R 10 are each independently: a hydrogen atom; or an alkyl group having 1 to 14 carbon atoms which may contain a heteroatom selected from an oxygen atom and a sulfur atom and may be substituted by a halogen atom, In formula (5), R 11 , R 12 , R 13 and R 14 are each independently: a hydrogen atom; or an alkyl group having 1 to 14 carbon atoms which may contain a heteroatom selected from an oxygen atom and a sulfur atom and may be substituted by a halogen atom, In formula (6), R 15 , R 16 , R 17 and R 18 are each independently: a hydrogen atom; or an alkyl group having 1 to 14 carbon atoms which may contain a heteroatom selected from an oxygen atom and a sulfur atom and may be substituted by a halogen atom, The average film thickness of the organic semiconductor single crystal film is 2 to 100 nm. At least a portion of a surface of the substrate in contact with the organic semiconductor single crystal film is hydrophobic, solvent-soluble, non-heat-resistant, or a combination thereof.

2. The organic semiconductor device according to claim 1, in, The area of ​​the organic semiconductor single crystal film is 2 mm 2 above.

3. The organic semiconductor device according to claim 1 or 2, in, The organic semiconductor single crystal film has a thickness of 0.005 mm 2 A single domain of continuous area above.

4. The organic semiconductor device according to claim 1 or 2, in, The organic semiconductor single crystal film has an average film thickness of 4 to 20 nm.

5. The organic semiconductor device according to claim 1 or 2, in, The organic semiconductor single crystal film has 1 to 5 molecular layers in the thickness direction.

6. The organic semiconductor device according to claim 1 or 2, in, The thickness of one molecular layer of the organic semiconductor single crystal film is 2 to 6 nm.

7. A method for producing an organic semiconductor single crystal film, It is characterized in that Include: A step of forming an organic semiconductor single crystal film having an average film thickness of 2 to 100 nm on a hydrophilic and water-insoluble first substrate by a coating method; and applying water to the interface between the first substrate and the organic semiconductor single crystal film to separate the organic semiconductor single crystal film from the first substrate, The organic semiconductor constituting the organic semiconductor single crystal film is a compound represented by the following formula (3), formula (4), formula (5) or formula (6): In formula (3), R 3 , R 4 , R 5 and R 6 are each independently: a hydrogen atom; or an alkyl group having 1 to 14 carbon atoms which may contain a heteroatom selected from an oxygen atom and a sulfur atom and may be substituted by a halogen atom, In formula (4), R 7 , R 8 , R 9 and R 10 are each independently: a hydrogen atom; or an alkyl group having 1 to 14 carbon atoms which may contain a heteroatom selected from an oxygen atom and a sulfur atom and may be substituted by a halogen atom, In formula (5), R 11 , R 12 , R 13 and R 14 are each independently: a hydrogen atom; or an alkyl group having 1 to 14 carbon atoms which may contain a heteroatom selected from an oxygen atom and a sulfur atom and may be substituted by a halogen atom, In formula (6), R 15 , R 16 , R 17 and R 18 Each independently represents: a hydrogen atom; or an alkyl group having 1 to 14 carbon atoms which may contain a hetero atom selected from an oxygen atom and a sulfur atom and may be substituted with a halogen atom.

8. The method for producing an organic semiconductor single crystal film according to claim 7, in, The area of ​​the organic semiconductor single crystal film is 2 mm 2 above.

9. The method for producing an organic semiconductor single crystal film according to claim 7 or 8, in, The contact angle of the first substrate is smaller than the contact angle of the organic semiconductor single crystal film, and the difference between the contact angles of the first substrate and the organic semiconductor single crystal film is greater than or equal to 80 degrees.

10. The method for producing an organic semiconductor single crystal film according to claim 7 or 8, in, The step of applying water to the interface between the first substrate and the organic semiconductor single crystal film includes the step of immersing the first substrate on which the organic semiconductor single crystal film is formed in water.

11. A method for manufacturing an organic semiconductor device, It is characterized in that Include: a step of arranging the organic semiconductor single crystal film produced by the method for producing an organic semiconductor single crystal film according to any one of claims 7 to 10 on a second substrate, At least a portion of a surface of the second substrate in contact with the organic semiconductor single crystal film is hydrophobic, solvent-soluble, non-heat-resistant, or a combination thereof.

12. The method for manufacturing an organic semiconductor device according to claim 11, in, The step of disposing the organic semiconductor single crystal film on the second substrate includes the following steps: The second substrate is arranged to be in contact with the organic semiconductor single crystal film formed on the first substrate, and water is applied to the interface between the first substrate and the organic semiconductor single crystal film to separate the organic semiconductor single crystal film from the first substrate and arrange it on the second substrate.

13. The method for manufacturing an organic semiconductor device according to claim 11 or 12, in, At least one of a concave portion, a convex portion, a concavo-convex portion, and an electrode is provided on at least a portion of a surface of the second substrate that is in contact with the organic semiconductor single crystal film.

Images