JP5050480B2 - ORGANIC SEMICONDUCTOR TRANSISTOR ELEMENT, ITS MANUFACTURING METHOD, SEMICONDUCTOR DEVICE, AND DISPLAY ELEMENT - Google Patents

Description

  The present invention relates to an organic semiconductor transistor element using an organic semiconductor, a manufacturing method thereof, a semiconductor device, and a display element.

Thin film transistors are widely used as display switching elements such as liquid crystal display elements. Conventionally, a thin film transistor is manufactured using amorphous or polycrystalline silicon. However, manufacturing of a thin film transistor using such silicon uses sputtering, a CVD apparatus, and other manufacturing processes using a vacuum system, which are very expensive. In addition, the manufacturing process of a vacuum system is repeatedly performed to form a thin film transistor, and each layer such as a semiconductor layer is formed. Therefore, an increase in the size of a display device using a thin film transistor has a problem with a significant increase in manufacturing cost. It was.
In addition, the process for forming amorphous or polycrystalline silicon is performed at a very high temperature, and the materials used as the base material are limited. Therefore, there is a problem that a resin substrate having a light weight and flexibility cannot be used.

On the other hand, research on organic semiconductors typified by organic EL elements has been actively conducted in recent years. At the same time, studies have been reported to incorporate organic materials into circuits that have characteristics of lightness and flexibility that are not found in silicon materials.
As an organic substance used for such a thin film transistor, a low molecular compound and a high molecular compound are used. As low molecular weight compounds, polyacene compounds such as pentacene and tetracene (for example, see Patent Documents 1 to 3) and phthalocyanine compounds such as copper phthalocyanine (for example, see Patent Document 4) have been proposed.

However, these polyacene compounds cause problems such as a low deposition rate during deposition when the molecular weight is large, and there is a problem that when the molecular weight is low, the vapor pressure becomes high and the film quality is deteriorated. It was difficult to form a thick film.
In addition, the properties such as conductivity and semiconductivity required when a device is formed using these compounds as an active layer largely depend not only on the purity of the material but also on crystallinity and orientation. For example, pentacene has a high crystallinity but is insoluble in a solvent, so it is formed by a vacuum deposition method. However, it is easily deteriorated by oxygen and moisture in the air, and needs to be handled with care.

  On the other hand, although the phthalocyanine compound has a low deposition temperature of 125 ° C. to 175 ° C., for example, there is a problem that the flatness of the formed film is poor and the carrier mobility is also poor.

  Examples of the polymer compound include aromatic oligomers such as sexithiophene (see, for example, Patent Document 5), polymer compounds such as polythiophene, polythienylene vinylene, and poly (p-phenylene vinylene) (for example, Patent Documents 6 to 9, Non-Patent Document 1) has been proposed.

Such a polymer compound is highly soluble and can be formed by a low-cost technique such as spin coating or dip coating, which is advantageous in the manufacturing process, but has a problem of low carrier mobility. It was. In addition, since poly (p-phenylene vinylene) is heat-treated after spin-coating a soluble precursor, there is a problem that defects tend to occur in the main chain conjugated polymer and the electrical properties are remarkably lowered.
Japanese Patent Laid-Open No. 5-05568 JP-A-10-270712 JP 2001-094107 A Japanese Patent Laid-Open No. 10-093104 JP-A-8-264805 JP-A-8-228034 JP-A-8-228035 Japanese Patent Laid-Open No. 10-125924 Japanese Patent Laid-Open No. 10-190001 Appl. Phys. Lett. , Vol. 73, 108 (1998)

  The present invention has been made in view of the above problems, and an object of the present invention is an organic semiconductor transistor element capable of forming a flat organic semiconductor, having a high operation speed, and easy to manufacture, and a method for manufacturing the same. And providing a semiconductor device and a display element using the organic semiconductor transistor element.

The above-mentioned subject is achieved by the following present invention. That is, the present invention
<1> A source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field An organic semiconductor transistor element including at least the organic semiconductor containing at least one selected from compounds represented by the following general formula (I):

(In General Formula (I), the bonding positions of two benzothiophene rings are 2-position and 2-position or 3-position and 3-position, and R ^{1 to} R ⁸ are each independently a hydrogen atom or unsubstituted. Represents an alkyl group having 1 to 3 carbon atoms .)

<2> a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field The semiconductor device includes at least one organic semiconductor transistor element including at least one organic semiconductor transistor element selected from compounds represented by the following general formula (I).
<3> A method for producing an organic semiconductor transistor element, wherein an organic semiconductor is formed using at least one selected from compounds represented by the following general formula (I).

(In General Formula (I), the bonding positions of two benzothiophene rings are 2-position and 2-position or 3-position and 3-position, and R ^{1 to} R ⁸ are each independently a hydrogen atom or unsubstituted. Represents an alkyl group having 1 to 3 carbon atoms .)

<4> The method for producing an organic semiconductor transistor element according to <3>, wherein the organic semiconductor is formed by vacuum deposition of at least one selected from the compounds represented by the general formula (I). It is.
<5> At least, a display element in which a state exhibiting the first color and a state exhibiting the second color change reversibly, a source electrode, a drain electrode, and the source electrode and the drain electrode can be electrically connected. At least a provided organic semiconductor and a gate electrode that is insulated from the organic semiconductor and capable of applying an electric field, and the organic semiconductor is selected from the compounds represented by the general formula (I) An organic semiconductor transistor element containing at least one kind. A display device characterized by comprising:
<6> The display device according to <5>, wherein the display element includes a display layer including charge-transfer particles that exhibit color developability according to a dispersed state.
<7> The display device according to <6>, wherein the charge transfer particles are metal particles having a plasmon coloring function.

  According to the present invention, an organic semiconductor transistor element that can form a flat organic semiconductor, has a high operating speed, and is easy to manufacture, a manufacturing method thereof, and a semiconductor device and a display element using the organic semiconductor transistor element Can be provided.

-Organic semiconductor transistor element-
The organic semiconductor transistor element of the present invention can be applied to a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and an electric field insulated from the organic semiconductor. And at least one selected from compounds represented by the following general formula (I) (hereinafter referred to as “benzothiophene compound” as appropriate): .
Since the benzothiophene compound is excellent in thermal stability during operation and film forming property and has high carrier mobility, the organic semiconductor transistor element of the present invention containing the benzothiophene compound has a flat organic semiconductor. Fast operating speed and easy to manufacture.

In general formula (I), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group Or a substituted or unsubstituted aralkyl group.

  As an alkyl group, a C1-C12 alkyl group is mentioned, C1-C6 is more preferable, and C1-C3 is still more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a hexyl group, and an octyl group.

  As an aryl group, a C6-C18 aryl group is mentioned, C6-C12 is more preferable. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, and a phenanthrene group.

  Examples of the aralkyl group include aralkyl groups having 7 to 20 carbon atoms, and 7 to 8 is more preferable. Examples of the aralkyl group include benzyl group and phenethyl group.

In general formula (I), R _1, R _2, R _3, R _4, R _5, R _6, R ₇ and R ₈ are preferably hydrogen atoms, and the bonding position is the 2nd or 3rd position. Is preferred.

Specific examples of the compound represented by the general formula (I) are shown in Table 1 together with the bonding positions of R _{1 to} R ₈ and the benzothiophene in the general formula (I).

  The benzothiophene compound can be synthesized, for example, as follows, but is not limited thereto.

  Unsubstituted and substituted Benzo [b] thiophene and Amberlite CG-120 (H type) are heated and stirred at 100 to 150 ° C. for 15 to 100 hours. The obtained compound can be purified by silica gel column chromatography and recrystallization to obtain a compound of the general formula (I).

As a method for forming an organic semiconductor, a vacuum deposition method, a molecular beam epitaxial growth method, or the like can be used. To form a flat organic semiconductor, the organic semiconductor is vacuum-deposited while being maintained at 150 to 200 ° C. It is desirable to form by this.

-Configuration of organic semiconductor transistor element, manufacturing method, etc.-
Next, the configuration of the organic semiconductor transistor element of the present invention using the above-described benzothiophene compound will be described in detail with specific examples.
The organic semiconductor transistor element of the present invention can be applied to a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and an electric field insulated from the organic semiconductor. A possible gate electrode.
Here, the organic semiconductor includes at least one benzothiophene compound described above. In addition, although the shape of the organic semiconductor transistor element of this invention can be made into a desired shape as needed, it is preferable that it is a thin film form.

Hereinafter, the configuration of the organic semiconductor transistor element of the present invention will be described in more detail with reference to the drawings, but is not limited thereto.
1 to 3 are schematic cross-sectional views showing an example of the configuration of the organic semiconductor transistor element of the present invention. Here, FIGS. 1 and 2 show a case where the organic semiconductor transistor element of the present invention has a field effect transistor structure. FIG. 3 shows a case where the organic semiconductor transistor element of the present invention has a static induction transistor (Static Induction Transistor) structure.

1 to 3, members having the same functions are denoted by the same reference numerals, 1 being a substrate, 2 being a source electrode, 3 being a drain electrode, 4 being an organic semiconductor layer, 5 being a gate electrode, and 6 being insulating. Represents a layer. Hereinafter, the configuration of the organic semiconductor transistor element of the present invention shown in FIGS.
In the organic semiconductor transistor element of the present invention shown in FIG. 1, a gate electrode 5 and an insulating layer 6 are provided in this order on a substrate 1, and the source electrode 2 and the drain electrode 3 are separated from each other on the insulating layer 6. The organic semiconductor layer 4 is provided so as to cover the source electrode 2 and the drain electrode 3.

In the organic semiconductor transistor element of the present invention shown in FIG. 2, a gate electrode 5 and an insulating layer 6 are provided in this order on a substrate 1, and a source electrode 2 and the source electrode 2 are formed on the insulating layer 6. The organic semiconductor layer 4 is provided so as to cover the surface opposite to the side in contact with the insulating layer 6. Further, the drain electrode 3 is provided on the surface of the organic semiconductor layer 4 opposite to the side on which the insulating layer 6 is provided, at a position separated from the source electrode 2 in the planar direction of the substrate 1.
Further, in the organic semiconductor transistor element of the present invention shown in FIG. 3, a source electrode 2, an organic semiconductor layer 4, and a drain electrode 3 are stacked in this order on a substrate 1, and a plurality of gate electrodes 5 are formed in the organic semiconductor layer 4. (In the example shown in FIG. 3, four gate electrodes 5 are arranged in parallel with the planar direction of the substrate 1 and at equal intervals).

The gate electrode 5 is arranged in a direction perpendicular to the paper surface so as to be parallel to both the source electrode 2 and the drain electrode 3, and the gate electrodes 5 are also provided so as to be parallel to each other. Yes. In FIG. 3, the gate electrode 5 and the organic semiconductor layer 4 are insulated by an insulating layer (not shown) provided at the interface between them.
In the organic semiconductor transistor element as shown in FIGS. 1 to 3, the current flowing between the source electrode 2 and the drain electrode 3 can be controlled by the voltage applied to the gate electrode 5.

  In addition, when producing any electronic device using the organic semiconductor transistor element of the present invention, it is used as a configuration (semiconductor device) in which one or more organic semiconductor transistor elements of the present invention are mounted on a substrate. A desired electronic device can be manufactured by combining this semiconductor device with another element or circuit.

Next, each member which comprises the organic-semiconductor element and semiconductor device of this invention except an organic-semiconductor part is demonstrated in detail.
As an electrode material used for the source electrode, the drain electrode, and the gate electrode, a material capable of efficiently injecting charges is used. Specifically, a metal, a metal oxide, a conductive polymer, or the like is used.
Examples of the metal include magnesium, aluminum, gold, silver, copper, chromium, tantalum, indium, palladium, lithium, calcium, and alloys thereof. Examples of the metal oxide include metal oxide films such as lithium oxide, magnesium oxide, aluminum oxide, indium tin oxide (ITO), tin oxide (NESA), indium oxide, zinc oxide, and indium zinc oxide.

Examples of the conductive polymer include polyaniline, polythiophene, polythiophene derivatives, polypyrrole, polypyridine, and a complex of polyethylenedioxythiophene and polystyrene sulfonic acid.
In addition, if the difference in ionization potential between the material used for the electrode and the above-described benzothiophene compound used for the organic semiconductor (layer) is large, the charge injection characteristics are deteriorated. Therefore, the material used for the drain electrode and / or the source electrode The difference in ionization potential between the ionization potential and the benzothiophene compound used for the organic semiconductor (layer) is preferably within 1.0 eV, more preferably within 0.5 ev. In view of the difference in ionization potential between the electrode and the benzothiophene compound, it is particularly preferable to use Au as the electrode material.

  As a method for forming an electrode, a thin film produced by using a known thin film forming method such as a vapor deposition method or sputtering as the electrode material described above is formed using a known photolithography method or a lift-off method, or an inkjet or the like. Thus, a method of etching into a desired pattern (electrode shape) using a resist or a method of directly transferring an electrode material such as aluminum can be used. When a conductive polymer is used as the electrode material, it may be dissolved in a solvent and patterned by ink jet or the like.

  Insulating members that insulate between each electrode or between the gate electrode and the organic semiconductor (layer) include inorganic substances such as silicon dioxide, silicon nitride, tantalum oxide, aluminum oxide, titanium oxide, polycarbonate resin, polyester resin, methacrylic resin, acrylic Resin, polyvinyl chloride resin, cellulose resin, urethane resin, epoxy resin, polystyrene styrene resin, polyvinyl acetate resin, styrene butadiene copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer Examples thereof include, but are not limited to, organic insulating polymers such as silicon resin.

  As the substrate, silicon single crystal or glass doped with a high concentration of phosphorus, etc., polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, cellulose resin, urethane resin, epoxy resin, police styrene resin, polyvinyl acetate Examples thereof include, but are not limited to, resins, styrene butadiene copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, plastic substrates such as silicone resins, and the like.

  In particular, when the organic semiconductor transistor element of the present invention is used in an electronic circuit used in an electronic device (hereinafter referred to as “flexible electronic device”) that is required to be flexible, such as electronic paper, digital paper, or portable electronic equipment. It is desirable to use a flexible substrate as the substrate. In particular, by using a substrate having a flexural modulus of 1000 MPa or more, more preferably 5000 MPa or more as the substrate, the substrate can be applied to a flexible display element drive circuit or electronic circuit.

  The organic semiconductor transistor element of the present invention has elasticity because the organic semiconductor portion contains the benzothiophene compound as a main component as described above, and even if the element is formed on a flexible substrate, It can withstand repeated deformation and maintain stable performance. On the other hand, in an inorganic semiconductor transistor element, since a semiconductor portion is made of an inorganic material, it lacks elasticity and is extremely difficult to use on the assumption of such deformation. Further, the process for manufacturing the inorganic semiconductor transistor element has a disadvantage that plastic cannot be used for the substrate because it requires a high temperature.

  In the present invention, the term “flexible electronic device” refers to [1] a usage state from a flat state regardless of whether the power is on or off, such as the electronic paper or digital paper described above. It can be bent, bent, bent, or vice versa. [2] The substrate is provided with one or more components on the substrate. [3] means an electronic device that is required to be flexible at least in the substrate portion provided with the organic semiconductor transistor element as described in the above item [1].

  The use of the organic semiconductor transistor element of the present invention and the semiconductor device using the same is not particularly limited, but electronic paper or digital paper, an organic EL element, an electrophoretic display element, a drive circuit for a display element such as a liquid crystal element, and an electronic tag It can be suitably used in the fields of theoretical circuits, memory elements, gas sensors and the like used for smart cards and the like.

-Display device-
The display device of the present invention includes at least a display element in which a state exhibiting the first color and a state exhibiting the second color change reversibly and the organic semiconductor transistor element of the present invention. In the display device of the present invention, an organic semiconductor transistor element is provided as a part of a display element drive circuit, and the display element is driven by the organic semiconductor transistor element.

  Examples of the display element include CRT (cathode ray tube), PDP (plasma display), ELD (electroluminescent display), VFD (vacuum fluorescent display), and fluorescent display tube (LED). (Light emitting diode: light emitting diode), LCD (liquid crystal display: liquid crystal display), ECD (electrochemical display: electrochemical display), EPID (electrophoretic image display: electrophoretic display), SPD (suspension display) Article display: dispersed particle orientation type display), TBD (twisting ball display: colored particle rotation type display), PLZT (transparent ceramic display: PLZT display), DMD (digital micromirror device), etc. Can be used.

  Here, an example in which a display element having a display layer containing charge-moving particles exhibiting color developability according to a dispersion state is applied to the display device of the present invention will be described with reference to the drawings. “Exhibiting color developability in accordance with the dispersed state” means exhibiting a hue that can be visually observed in a state where the charge transfer particles are dispersed.

  FIG. 4 is a schematic configuration diagram showing an example of the display device of the present invention. FIG. 5 is a schematic configuration diagram showing another example of the display device of the present invention.

  A display device 100 shown in FIG. 4 includes an organic semiconductor transistor element 10 and a display element 20 stacked on the organic semiconductor transistor element 10 with an interlayer insulating layer 40 interposed therebetween.

  In the organic semiconductor transistor element 10, a gate electrode 12, a gate insulating layer 13, and an organic semiconductor layer 14 are provided in this order on a substrate 11, and the source electrode 15 and the drain electrode 16 are separated from each other on the organic semiconductor layer 14. Is provided.

  The display element 20 includes a transparent display substrate 21 provided on the viewing direction side, a back substrate 22 facing the display substrate 21 with a gap, and a gap member 23 for holding the substrates at a predetermined interval. It has. Electrodes 24 and 25 are disposed on the opposing surface sides of the display substrate 21 and the back substrate 22.

  In the display substrate 21, the back substrate 22, and the gap member 23, the first charge transfer particles 26A (for example, white particles) and the second charge transfer particles 26B (colors different from the first charge transfer particles 26A) For example, a microcapsule 27 holding black particles) and a dispersion medium 28 (for example, a matrix resin) are enclosed to constitute a display layer 29.

  The display element 20 having such a configuration moves one of the first charge-moving particles 26A and the second charge-moving particles 26B held in the microcapsule 27 to the display surface side by electrophoresis. The color of each particle (for example, white or black) can be displayed.

  The display element 20 and the organic semiconductor transistor element 10 are electrically connected to the electrode 25 of the display element 20 and the drain electrode 16 of the organic semiconductor transistor element 10 by a metal wire 41 (for example, Au wire).

  On the other hand, the display device 101 shown in FIG. 5 also includes the organic semiconductor transistor element 10 and the display element 30 stacked on the organic semiconductor transistor element 10 with an interlayer insulating layer 41 interposed therebetween. The organic semiconductor transistor element 10 has the same configuration as that shown in FIG.

  The display element 30 includes a transparent display substrate 31 provided on the viewing direction side, a back substrate 32 facing the display substrate 31 with a gap, and a gap member 33 for holding the substrates at a predetermined interval. It has. Electrodes 34 and 35 are disposed on the opposing surface sides of the display substrate 31 and the back substrate 32.

  Within the display substrate 31, the back substrate 32, and the gap member 33, charge-transfer particles 36 (for example, metal particles having a plasmon coloring function), and charge-mobility particles having a mobility lower than that of the charge-transfer particles 36. Isomeric particles 37 (for example, white particles) exhibiting a lightness color lower than the presentable lightness range of 36 and a dispersion medium 38 (for example, an insulating liquid) are enclosed to constitute a display layer 39.

  The display element 30 having such a configuration displays the color exhibited by the charge mobile particles 36 by moving the charge mobile particles 36 to the display surface side by electrophoresis, and displays the charge mobile particles 36 on the back side. The color exhibited by the isomeric particle 37 can be displayed by moving to.

  The display element 30 and the organic semiconductor transistor element 10 are electrically connected to the electrode 35 of the display element 30 and the drain electrode 16 of the organic semiconductor transistor element 10 by a metal wire (for example, Au wire).

  Here, the charge transfer particles will be briefly described. Any charge transfer particles can be used as long as they are used in electrophoresis. For example, black pigment particles such as carbon black, manganese ferrite black, and titanium black can be used as the black particles. As the white particles, white pigment particles such as titanium oxide, zinc oxide, and tin oxide can be used. Further, as other colored particles, metal particles having a plasmon coloring function, particularly metal colloid particles, can be used from the viewpoint of colorability and stability.

  The metal constituting the metal colloidal particles includes noble metal or copper (hereinafter collectively referred to as “metal”), and the noble metal is not particularly limited. For example, gold, silver, ruthenium, rhodium, Palladium, osmium, iridium, platinum, etc. can be mentioned. Among the metals, gold, silver and platinum are preferable.

  The metal colloidal particles can be prepared by chemical methods that reduce metal ions to form nanoparticles through metal atoms and metal clusters, or cold trap the metal that has become particles by evaporating bulk metal in an inert gas. For example, a physical method is known in which a metal thin film is formed by vacuum trapping or forming a metal thin film on the polymer thin film, followed by heating to break the metal thin film and dispersing the metal particles in the polymer in a solid state. The chemical method does not require the use of a special apparatus and is advantageous for the preparation of the metal colloidal particles of the present invention. Therefore, general examples will be described later, but the present invention is not limited thereto.

  In addition, about another structure, a well-known structure is applicable.

  As described above, the organic semiconductor transistor element of the present invention can be applied to various display elements.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the present invention.

Example 1
A CrMo film having a thickness of 150 nm was formed on a Corning 1737 glass substrate by a sputtering method to obtain a gate electrode. Next, an SiO ₂ film having a thickness of 300 nm was formed on the gate electrode by a CVD method to form a gate insulating film. In addition, the exemplified compound 1 was deposited by vapor deposition (device name: VPC-1100 (manufactured by Vacuum Kiko Co., Ltd.), conditions: film forming rate: 5-8 nm / s pressure: 1.3 × 10 ⁻⁴ Pa). A film was formed. At this time, the film formation temperature was 160 ° C., and the film thickness was 50 nm. Further, gold was formed to a thickness of 150 nm by a sputtering method, and patterned by a photolithography process to form a source electrode and a drain electrode. Thereafter, a polyimide (CT4112A manufactured by Kyocera Chemical) precursor was spin-coated and annealed at 130 ° C. to produce an organic semiconductor transistor element as an interlayer insulating film. The channel length of the organic semiconductor transistor element thus fabricated was 18 μm and the channel width was 400 μm.

(Example 2)
An organic semiconductor transistor element was produced in the same manner as in Example 1 except that the exemplified compound (2) was used instead of the exemplified compound (1) used in Example 1.

(Example 3)
An organic semiconductor transistor element was produced in the same manner as in Example 1 except that the exemplified compound (3) was used instead of the exemplified compound (1) used in Example 1.

Example 4
An organic semiconductor transistor element was produced in the same manner as in Example 1 except that the exemplified compound (4) was used instead of the exemplified compound (1) used in Example 1.

(Comparative Example 1)
Pentacene is used in place of the exemplified compound (1) used in Example 1 above, the deposition temperature is 250 ° C., and the deposition method (device name: VPC-1100 (manufactured by Vacuum Kiko Co., Ltd.), conditions: film formation) An organic semiconductor transistor element was produced in the same manner as in Example 1 except that the organic semiconductor was formed at a rate of 5 to 8 nm / s pressure: 1.3 × 10 ⁻⁴ Pa).

(Comparative Example 2)
Tetracene was used in place of the exemplified compound (1) used in Example 1 above, the film formation temperature was set to 270 ° C., and the vapor deposition method (device name: VPC-1100 (manufactured by Vacuum Kiko Co., Ltd.)), conditions: film formation rate : 5-8 nm / s Pressure: 1.3 × 10 ⁻⁴ Pa) An organic semiconductor transistor element was produced in the same manner as in Example 1 except that the organic semiconductor was formed.

(Comparative Example 3)
Instead of the exemplified compound (1) used in Example 1 above, copper phthalocyanine, which is a phthalocyanine-based compound, was used, and the deposition temperature was set to 70 ° C. (device name: VPC-1100 (manufactured by Vacuum Kiko Co., Ltd.)) The organic semiconductor transistor device was manufactured in the same manner as in Example 1 except that the organic semiconductor was formed under the conditions: film forming rate: 5 to 8 nm / s pressure: 1.3 × 10 ⁻⁴ Pa).

(Comparative Example 4)
Instead of the exemplified compound (1) used in Example 1 above, α-ω-hexathiophene was used, and the deposition temperature was set to 100 ° C. ((device name: VPC-1100 (manufactured by Vacuum Kiko Co., Ltd., An organic semiconductor transistor element was produced in the same manner as in Example 1 except that the organic semiconductor was formed under the conditions: film formation rate: 5 to 8 nm / s pressure: 1.3 × 10 ⁻⁴ Pa).

(Comparative Example 5)
The same procedure as in Example 1 was performed except that poly (3-hexylthiophene), which is polythiophene, was used instead of the exemplified compound (1) used in Example 1 above, and an organic semiconductor was formed by a spin coater method (solvent: chlorobenzene). Thus, an organic semiconductor transistor element was produced.

-Evaluation-
The organic semiconductor transistor elements obtained in Examples and Comparative Examples were measured for current-voltage characteristics when a gate voltage was applied using a semiconductor parameter analyzer (manufactured by Agilent Technologies, 4155C), and carrier mobility (linear region) ) And the on / off ratio were calculated.
Further, the surface roughness Ra was measured according to JIS B0601 (2001) using a surface roughness shape measuring instrument (Surfcom Co., Ltd. 1400A series manufactured by Tokyo Seimitsu). Specifically, the measurement was performed under the conditions of a measurement length of 2.5 mm, a cutoff wavelength of 0.8 mm, and a measurement speed of 0.60 mm / s.

  Organic semiconductor defects were evaluated by AFM (Atomic Force Microscope) under atmospheric conditions.

  Table 2 shows the film quality, on / off ratio, and carrier mobility of the charge transporting material used to form the organic compound, together with the film formation temperature of the organic semiconductor. In addition, the presence or absence of defects in the organic semiconductor transistor element is shown.

As can be seen from Table 2, it was found that the surface roughness Ra was smaller in the example and the film formability was better.
The organic semiconductor transistor elements shown in any of the examples show switching characteristics in which the drain-source current flowing between the source electrode, the organic semiconductor layer, and the drain electrode changes with the change of the voltage applied to the gate electrode (gate voltage), It showed a good on / off ratio.
However, in the comparative example, it was found that the on / off ratio was inferior to the device of the example because the carrier mobility of the charge transporting material used for forming the organic semiconductor was low.

(Example 5)
As shown below, a display device having the same configuration as that of the display device shown in FIG. 4 was produced.
First, an organic semiconductor transistor element was produced in the same manner as in Example 1.
On the other hand, titania particles (manufactured by Ishihara Sangyo Co., Ltd.) surface-treated with a titania-based coupling agent (KR-TTS made by Ajinomoto Co., Ltd.) and an aluminum-based coupling agent (AL-M made by Ajinomoto Co.) are dispersed in dodecylbenzene (manufactured by Kanto Chemical). Further, an anthraquinone dye (manufactured by Chuo Synthetic Chemical) was added and dispersed. This dispersion was dropped into a solution in which gum arabic and gelatin were dissolved, and the mixture was stirred at a rotational speed of 1300 rpm.

  Next, the pH of the solution was adjusted to 3.7 with acetic acid, and then the capsules were precipitated by ice cooling. Further, formaldehyde was added to form a crosslinked structure in the capsule. Thereafter, stirring was continued for a whole day and night, and then classification was performed to prepare microcapsules having a particle size of 50 to 60 μm. The prepared microcapsules, a water-based emulsion type binder material (manufactured by Shin-Etsu Chemical Co., “Polon”) and water were mixed to prepare a microcapsule dispersion in which the microcapsules and the binder material were dispersed in water. At this time, the concentration of the binder material in the microcapsule dispersion was 5 wt%.

  The prepared microcapsule dispersion is applied on a glass substrate with a transparent electrode ITO (thickness 0.7 mm) by a doctor blade method, thereby displaying a display layer having a thickness of 60 μm (approximately the same thickness as the average particle diameter of the microcapsules). After forming, the glass on which ITO was formed was laminated. In this way, a display element was produced.

  The obtained display element was bonded onto the organic semiconductor transistor element, and ITO and the drain electrode were connected by an Au wire to produce a display device. In the display element in this display device, white display and black display can be arbitrarily switched by adjusting a combination of a voltage from the power source connected to the gate electrode and a voltage from the power source connected to the source electrode. done.

(Example 6)
As shown below, a display device having the same configuration as the display device shown in FIG. 5 was produced.
First, an organic semiconductor transistor element was produced in the same manner as in Example 1.
On the other hand, ITO is deposited on a glass substrate having a thickness of 0.7 mm by a sputtering method to a thickness of 50 nm, and then a layer for barrier ribs is formed by coating using a photo-tourism polyimide varnish. A partition wall having a height of 50 μm and a width of 20 μm was formed. Thereafter, an adhesive layer is formed on the partition walls, and then filled with a colloidal gold ethanol solution (volume average particle diameter 20 nm) containing white particles (titanium oxide, volume average particle diameter 10 μm), and then ITO is deposited on the glass. A display element was manufactured by applying heat to the substrate and bonding the substrates together.

  The obtained display element was bonded onto the organic semiconductor transistor, and ITO and the drain electrode were connected by an Au wire to produce a display device. In the display element in this display device, the colloidal gold particles are in a dispersed state and show a red color, but from the voltage (-50 V) from the power source connected to the gate electrode and the power source connected to the source electrode The gold colloidal particles moved to the lower electrode side by the combination of the voltage (30V) of and were observed as the color of white particles, that is, white.

(Comparative Example 6)
In Example 6, a display element was produced in the same manner as in Example 6 except that pentacene was used instead of the exemplified compound 1.
This display element was in a state in which colloidal gold particles were dispersed and showed a red color, but the same voltage as in Example 6, that is, the voltage (-50 V) from the power source connected to the gate electrode, and the source Due to the combination of the voltage (30 V) from the power source connected to the electrode, the display element remained red and no change was observed.

It is the schematic block diagram which showed an example of the laminated constitution of the organic-semiconductor transistor element of this invention. It is the schematic block diagram which showed an example of the laminated constitution of the organic-semiconductor transistor element of this invention. It is the schematic block diagram which showed an example of the laminated constitution of the organic-semiconductor transistor element of this invention. It is the schematic block diagram which showed an example of the structure of the display apparatus using the organic-semiconductor transistor element of this invention. It is the schematic block diagram which showed an example of the structure of the display apparatus using the organic-semiconductor transistor element of this invention.

Explanation of symbols

1 substrate 2 source electrode 3 drain electrode 4 organic semiconductor layer 5 gate electrode 6 insulating layer

Claims (7)

At least a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field; This organic semiconductor contains at least 1 sort (s) selected from the compound shown by the following general formula (I), The organic-semiconductor transistor element characterized by the above-mentioned.


(In General Formula (I), the bonding positions of two benzothiophene rings are 2-position and 2-position or 3-position and 3-position, and R ^{1 to} R ⁸ are each independently a hydrogen atom or unsubstituted. Represents an alkyl group having 1 to 3 carbon atoms .) At least a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field; The semiconductor device which has one or more organic-semiconductor transistor elements in which this organic semiconductor contains at least 1 sort (s) selected from the compound shown by the following general formula (I).


(In General Formula (I), the bonding positions of two benzothiophene rings are 2-position and 2-position or 3-position and 3-position, and R ^{1 to} R ⁸ are each independently a hydrogen atom or unsubstituted. Represents an alkyl group having 1 to 3 carbon atoms .) The manufacturing method of an organic-semiconductor transistor element characterized by forming an organic semiconductor using at least 1 sort (s) selected from the compound shown by the following general formula (I).


(In General Formula (I), the bonding positions of two benzothiophene rings are 2-position and 2-position or 3-position and 3-position, and R ^{1 to} R ⁸ are each independently a hydrogen atom or unsubstituted. Represents an alkyl group having 1 to 3 carbon atoms .)   4. The method for producing an organic semiconductor transistor element according to claim 3, wherein the organic semiconductor is formed by vacuum deposition of at least one selected from the compounds represented by the general formula (I). At least a display element in which a state exhibiting the first color and a state exhibiting the second color change reversibly;
At least a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the organic semiconductor and capable of applying an electric field; organic semiconductors, display device characterized by having a an organic semiconductor transistor element characterized by containing at least one selected from compounds represented by the following general formula (I).


(In general formula (I), the bonding positions of two benzothiophene rings are 2-position and 2-position or 3-position and 3-position, and R ^{1 to} R ⁸ are each independently a hydrogen atom or unsubstituted. Represents an alkyl group having 1 to 3 carbon atoms.)   The display device according to claim 5, wherein the display element includes a display layer including charge transfer particles that exhibit color developability according to a dispersion state.   The display device according to claim 6, wherein the charge transfer particles are metal particles having a plasmon coloring function.