WO2007026781A1 - トランジスタ及びその製造方法、並びに、このトランジスタを有する半導体装置 - Google Patents
トランジスタ及びその製造方法、並びに、このトランジスタを有する半導体装置 Download PDFInfo
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- WO2007026781A1 WO2007026781A1 PCT/JP2006/317133 JP2006317133W WO2007026781A1 WO 2007026781 A1 WO2007026781 A1 WO 2007026781A1 JP 2006317133 W JP2006317133 W JP 2006317133W WO 2007026781 A1 WO2007026781 A1 WO 2007026781A1
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- WIPO (PCT)
- Prior art keywords
- active layer
- transistor
- semiconductor film
- insulating layer
- manufacturing
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/762—Charge transfer devices
- H01L29/765—Charge-coupled devices
- H01L29/768—Charge-coupled devices with field effect produced by an insulated gate
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/191—Deposition of organic active material characterised by provisions for the orientation or alignment of the layer to be deposited
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/464—Lateral top-gate IGFETs comprising only a single gate
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/491—Vertical transistors, e.g. vertical carbon nanotube field effect transistors [CNT-FETs]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/80—Constructional details
- H10K10/82—Electrodes
- H10K10/84—Ohmic electrodes, e.g. source or drain electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/50—Forming devices by joining two substrates together, e.g. lamination techniques
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/80—Manufacture or treatment specially adapted for the organic devices covered by this subclass using temporary substrates
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
Definitions
- the present invention relates to a transistor, a method for manufacturing the same, and a semiconductor device having the transistor.
- a field effect transistor which is one of these transistors, generally has a structure in which a gate electrode is provided via an insulating layer on a layer (active layer) made of a semiconductor material to which a source electrode and a drain electrode are connected.
- organic transistors using an organic semiconductor compound in the active layer have the advantage of being lightweight and flexible, and are expected to be applied to various electronic devices.
- the active layer of the organic transistor is formed by depositing an organic semiconductor compound on the insulating layer provided on the substrate, or by spin coating, drop casting, or printing a solution containing the organic semiconductor compound. In many cases (Non-patent Document 1).
- Non-Patent Document 1 "Operational Technology for Organic Transistors", Technical Information Association, 2003
- Non-Patent Document 2 H. Sirringhaus et al., Appl. Phys. Lett., Vol 77, No. 3, p.406-408, 20 02
- Non-Patent Document 3 M. L. Swiggers et al., Appl. Phys. Lett., Vol 79, No. 9, p.1300-1302, 2001
- Non-Patent Document 4 H. Heil et al., Appl. Phys. Lett., Vol 93, No. 3, p.1636— 1641, 2003
- Patent Document 1 JP 2004-356422 A
- the above-described conventional method for producing an organic transistor aimed at improving carrier mobility by forming an active layer having orientation is a process for imparting orientation to the active layer even when V deviation occurs. Due to the complexity of the organic transistors, the production of organic transistors tended to be significantly more difficult than in the case where the active layer was not oriented.
- the present invention has been made in view of such circumstances, and an active layer having orientation can be formed by a simple method, and a transistor having excellent carrier mobility can be obtained.
- the purpose is to provide. It is another object of the present invention to provide an organic transistor having an active layer having orientation and high carrier mobility.
- a method for producing a transistor of the present invention is a method for producing a transistor having an active layer made of a semiconductor film containing an organic semiconductor compound, the step of stretching the semiconductor film, And a step of applying an active layer to the surface on which the active layer is formed while applying heat and Z or pressure to obtain the active layer.
- the organic semiconductor compounds constituting the semiconductor film by stretching are aligned in the stretching direction, so that a predetermined orientation can be imparted to the semiconductor film.
- an active layer oriented by simply stretching the semiconductor film can be obtained, and an active layer having an orientation can be easily formed as compared with the conventional method.
- the semiconductor film is attached to the surface on which the active layer is formed while heating and Z or pressurizing. For this reason, the active layer is in close contact with the layer adjacent to the active layer, and characteristics such as carrier mobility are favorably exhibited. It will be the saruchi of volcano.
- the step of stretching the semiconductor film is performed first, and the stretched semiconductor film may be pasted, and the unstretched semiconductor film is pasted first. Thereafter, this semiconductor film may be stretched.
- orientation is imparted at the time of forming the active layer or after the formation of the active layer, but the semiconductor film is pasted after stretching as in the former. In some cases, it is possible to give an appropriate orientation to the semiconductor film to be the active layer in advance, and it is easy to form an active layer having a desired orientation.
- the method for manufacturing a transistor of the present invention is a method for manufacturing a transistor having an active layer made of a semiconductor film containing an organic semiconductor compound, the step of aligning the semiconductor film,
- a step of attaching the semiconductor film to the surface on which the active layer is to be formed while applying heat and Z or pressure to form the active layer is possible to satisfactorily form an active layer oriented not only by stretching but by various methods by pasting a semiconductor film while heating and Z or pressurizing.
- the method for producing a transistor of the present invention is a method for producing a transistor having an active layer made of a semiconductor film containing an organic semiconductor compound, the step of stretching and aligning the semiconductor film, and the semiconductor A step of forming an active layer by applying a force to the surface on which the active layer is to be formed without applying heat and Z or pressure.
- the semiconductor film is attached to the surface with a working liquid interposed between the surface on which the active layer is formed.
- a working liquid interposed between the surface on which the active layer is formed.
- the method for manufacturing a transistor of the present invention is preferably applied to manufacture of a transistor having the following configuration. That is, the transistor manufacturing method of the present invention includes a source electrode and a drain electrode, an active layer made of a semiconductor film including an organic semiconductor compound serving as a current path between them, a gate electrode for controlling a current passing through the current path,
- a method for manufacturing a transistor having an insulating layer disposed between an active layer and a gate electrode comprising: a step of stretching a semiconductor film; and insulating the semiconductor film while heating and Z or pressurizing the semiconductor film. And a step of obtaining an active layer by laminating with the layer.
- the transistor manufacturing method of the present invention controls the source electrode and the drain electrode, an active layer made of a semiconductor film containing an organic semiconductor compound, serving as a current path between them, and a current passing through the current path.
- the method may include a step of attaching the insulating layer to obtain an active layer.
- the transistor manufacturing method of the present invention controls the current passing through the source electrode and the drain electrode, an active layer made of a semiconductor film containing an organic semiconductor compound, serving as a current path therebetween, and a current path.
- an oriented active layer can be easily formed by stretching a semiconductor film, and heating and Z or pressurization are performed during pasting.
- the active layer can be satisfactorily formed on the insulating layer.
- a transistor having high carrier mobility can be obtained.
- the semiconductor film is bonded to the insulating layer with a working liquid interposed between the insulating film and the insulating layer. By doing so, the bonding of the semiconductor film and the insulating layer is performed more satisfactorily. It is possible to further reduce the occurrence of deformation and defects of the transistor.
- the transistor having the above structure manufactured by the manufacturing method of the present invention has a layer having a compound force different from that of the organic semiconductor compound between the source electrode and the Z or drain electrode and the active layer. Is preferable.
- the contact resistance between the active layer containing an organic semiconductor compound and functioning as a carrier transport layer, and the source and drain electrodes can be reduced to further increase the carrier mobility. Is possible.
- the present invention also provides a transistor that can be obtained favorably by the method for producing a transistor of the present invention. That is, the transistor of the present invention has an active layer made of a semiconductor film containing an organic semiconductor compound, the active layer is made of a stretched semiconductor film, and the surface on which the semiconductor film forms an active layer. It is formed by pasting while heating and applying Z or pressure.
- the active layer of the active transistor is made of a stretched semiconductor film, it has a predetermined orientation.
- the active layer is formed by attaching a semiconductor film while heating or pressing the surface on which the active layer is formed, the active layer has good adhesion to the surface. It will be a thing. Therefore, the transistor of the present invention having such an active layer can exhibit excellent transistor characteristics with high carrier mobility and high interlayer adhesion.
- the transistor of the present invention has an active layer made of a semiconductor film containing an organic semiconductor compound, the active layer is made of an oriented semiconductor film, and the surface on which the semiconductor film forms the active layer is heated. And may be formed by being attached while applying Z or pressure.
- the semiconductor device includes an active layer made of a semiconductor film containing an organic semiconductor compound, the active layer is made of a stretched and oriented semiconductor film, and the semiconductor film is heated and applied to a surface on which the active layer is formed. It may be formed by being attached while applying Z or pressure.
- these transistors also have an orientation and an active layer excellent in adhesion to an adjacent surface is well formed, interlayer adhesion with high carrier mobility and high adhesion is achieved. It is possible to exhibit excellent transistor characteristics. Also, these transistors are preferably those in which an active layer is formed by pasting with a working solution in the same manner as described above.
- a transistor having the following configuration is particularly preferable. is there. That is, a source electrode and a drain electrode, an active layer made of a semiconductor film containing an organic semiconductor compound as a current path between them, a gate electrode for controlling a current passing through the current path, and an active layer and a gate
- the active layer is made of a stretched semiconductor film, and is formed by bonding the semiconductor film to the insulating layer while heating and z or pressurizing. It is preferable that it is.
- a source electrode and a drain electrode an active layer made of a semiconductor film including an organic semiconductor compound, which becomes a current path between them, a gate electrode for controlling a current passing through the current path, and an active layer
- the active layer is composed of an oriented semiconductor film and is bonded to the insulating layer while heating and Z or pressurizing the semiconductor film. Even if it was formed.
- the source electrode and the drain electrode an active layer made of a semiconductor film containing an organic semiconductor compound, serving as a current path between them, a gate electrode for controlling a current passing through the current path, and an active layer
- the active layer is composed of a semiconductor film oriented by stretching, and the semiconductor film is bonded to the insulating layer while heating and Z or pressurizing. It may be formed.
- These transistors also have an orientation similar to the transistor of the present invention described above, and have an active layer that has excellent adhesion to the adjacent surface, and therefore has high carrier mobility. Due to the high interlayer adhesion, excellent transistor characteristics can be exhibited.
- these transistors are preferably those in which an active layer is formed by bonding using a working solution. Furthermore, it is more preferable to have a layer having a compound strength different from that of the organic semiconductor compound between the active layer and the source electrode and the Z or drain electrode.
- the present invention also provides a semiconductor device having the transistor of the present invention.
- a semiconductor device having the transistor of the present invention.
- Such a semiconductor device can exhibit good characteristics due to the excellent transistor characteristics of the transistor of the present invention.
- a method for producing a transistor capable of forming an active layer having an orientation by a simple method and obtaining a transistor having excellent carrier mobility, and an active layer having an orientation It is possible to provide organic transistors with high carrier mobility It becomes.
- FIG. 1 is a schematic cross-sectional view of a transistor according to a first embodiment.
- FIG. 2 is a schematic cross-sectional view of a transistor according to a second embodiment.
- FIG. 3 is a schematic cross-sectional view of a transistor according to a third embodiment.
- FIG. 4 is a schematic cross-sectional view of a transistor according to a fourth embodiment.
- FIG. 5 is a schematic cross-sectional view of a transistor according to a fifth embodiment.
- FIG. 6 is a schematic cross-sectional view of a transistor according to a sixth embodiment.
- FIG. 7 is a process chart showing the method for manufacturing the transistor according to the first embodiment.
- FIG. 8 is a process diagram showing a method of manufacturing a transistor according to a second embodiment.
- FIG. 9 is a process diagram showing a method of manufacturing a transistor according to a third embodiment.
- FIG. 10 is a process diagram showing a method of manufacturing a transistor according to a fourth embodiment.
- FIG. 11 is a process diagram showing a method of manufacturing a transistor according to a fifth embodiment.
- FIG. 12 is a process diagram showing a method of manufacturing a transistor according to a fifth embodiment.
- FIG. 13 is a process diagram showing a method for manufacturing a transistor according to a sixth embodiment.
- FIG. 14 is a process diagram showing a method of manufacturing a transistor according to a sixth embodiment.
- FIG. 15 is a diagram showing manufacturing steps of transistors of Examples:! To 3;
- FIG. 16 is a diagram showing part of the manufacturing process of the transistor of Comparative Example 25.
- FIG. 17 is a schematic cross-sectional view of a transistor obtained in Example 4.
- FIG. 18 shows a part of the manufacturing process of the transistor of Example 6.
- stretched laminate 217 ... supported film after stretching, 218 ... a stretched poly (3-hexylthiophene) film, 220 ... an active layer after stretching, 228 ... an unstretched active layer, a layer of 500 --- 4- (trifluoromethyl) thiophenol.
- the present invention is a semiconductor element that amplifies or switches a current and includes an active layer containing an organic semiconductor compound. It can be applied without any particular restrictions.
- the transistor has a configuration including at least an active layer and another layer adjacent to the active layer, and the active layer is formed on a surface of the other layer on which the active layer is formed. It is a thing. Examples of such a transistor include a bipolar transistor, an electrostatic induction transistor, and a field effect transistor.
- a source electrode and a drain electrode an active layer that serves as a current path between these electrodes and contains an organic semiconductor compound
- a gate electrode that controls a current passing through the current path
- a transistor including an insulating layer disposed between an active layer and a gate electrode and a manufacturing method thereof will be described.
- the transistor having such a configuration for example, in the case of a field effect transistor, there are various types of structures such as a planar type, an inverted staggered type, and a staggered type.
- FIG. 1 is a schematic cross-sectional view of a transistor according to the first embodiment.
- the transistor 100 illustrated in FIG. 1 includes a substrate 10, a gate electrode 12 formed on the substrate 10, an insulating layer 14 formed on the substrate 10 so as to cover the gate electrode 12, and a gate electrode 12 formed on the insulating layer 14. And the active layer 20 formed on the insulating layer 14 so as to cover the source electrode 16 and the drain electrode 18.
- FIG. 2 is a schematic cross-sectional view of a transistor according to the second embodiment.
- Transistor shown in Figure 2 105 is insulated so as to cover the gate electrode 12, the insulating layer 14 formed on the gate electrode 12, the source electrode 16 and the drain electrode 18 formed on the insulating layer 14, and the source electrode 16 and the drain electrode 18. And an active layer 20 formed on the layer 14.
- the gate electrode 12 in the transistor 105 also functions as the substrate 10 in the transistor 100 of the first embodiment.
- FIG. 3 is a schematic cross-sectional view of a transistor according to the third embodiment. 3 includes a gate electrode 12, an insulating layer 14 formed on both surfaces of the gate electrode 12, a source electrode 16 and a drain electrode 18 formed on one insulating layer 14, and a source electrode 16 And an active layer 20 formed on the insulating layer 14 so as to cover the drain electrode 18 and a support film 52 formed on the active layer 20.
- the gate electrode 12 in the transistor 110 also functions as the substrate 10 in the transistor 100 of the first embodiment.
- FIG. 4 is a schematic cross-sectional view of a transistor according to the fourth embodiment.
- the transistor 115 shown in FIG. 4 includes a gate electrode 12, an insulating layer 14 formed on the gate electrode 12, an active layer 20 formed on the insulating layer 14, and a source electrode 16 formed on the active layer 20. And the drain electrode 18.
- FIG. 5 is a schematic cross-sectional view of a transistor according to the fifth embodiment.
- the transistor 120 is a static induction organic thin film transistor.
- the transistor 120 shown in FIG. 5 includes a substrate 10, a source electrode 16 formed on the substrate 10, an active layer 20 formed on the source electrode 16, and a plurality (four in this case) formed on the active layer 20.
- the two active layers 20 and 24 may be layers formed of the same material or different layers.
- FIG. 6 is a schematic cross-sectional view of a transistor according to the sixth embodiment.
- the transistor 125 includes a substrate 10, a source electrode 16 and a drain electrode 18 formed on the substrate 10, and an active layer 20 formed on the substrate 10 so as to cover the source electrode 16 and the drain electrode 18. And an insulating layer 14 formed on the active layer 20 and a gate electrode 12 formed on the insulating layer 14. It is to be prepared.
- the active layer 20 is a layer containing an organic semiconductor compound, and the current between the source electrode 16 and the drain electrode 18 is the same. It becomes a passage (channel).
- the gate electrode 12 controls a current passing through a current path (channel) in the active layer 20 by applying a voltage.
- the active layers 20 and 24 contain an organic semiconductor compound and form a current path between the source electrode 16 and the drain electrode 18.
- the gate electrode 12 controls the current passing through the current path in the same manner as described above.
- FIG. 7 is a process diagram showing the method of manufacturing the transistor according to the first embodiment.
- the substrate 10, the gate electrode 12 formed on the substrate 10, the insulating layer 14 formed on the substrate 10 so as to cover the gate electrode 12, and the insulating layer 14 are formed.
- An element substrate 30 having the source electrode 16 and the drain electrode 18 thus prepared is prepared (FIG. 7 (a)).
- a semiconductor film 22 to be the active layer 20 containing an organic semiconductor compound is prepared (FIG. 7 (b)).
- the substrate 10 a substrate that does not impair the characteristics as a field effect transistor is used, and examples thereof include a silicon substrate, a glass substrate, a plastic substrate, and a stainless foil substrate.
- the insulating layer 14 also has a material strength with high electrical insulation, and for example, acid silicon, silicon nitride, acid aluminum, acid tantalum, or an insulating polymer can be used.
- examples of the insulating polymer include polyimide, poly (butanol), polyester, methallyl resin, polycarbonate, polystyrene, and norylene.
- the surface of the insulating layer 14 may be physically and chemically modified by various methods. Examples of physical modification methods include treatment with ozone UV or O plasma.
- Examples of the chemical modification method include treatment with a surface treatment agent such as a silane coupling agent.
- Surface treatment agents include alkyl chlorosilanes, alkyl alkoxy silanes, fluorinated alkyl chloro silanes, fluorinated alkyl alkoxy Examples include silanes, silylamine compounds such as hexamethyldisilazane, and the like. This surface treatment can be performed, for example, by bringing the insulating layer 14 into contact with a solution or gas of the surface treating agent and adsorbing the surface treating agent on the surface of the insulating layer 14. Prior to the surface treatment, the surface of the insulating layer 14 to be surface treated can be treated with ozone UV or O plasma.
- Examples of the method for forming the insulating layer 14 on the substrate 10 include a plasma CVD method, a thermal evaporation method, a thermal oxidation method, an anodic oxidation method, a spin coating method, a casting method, a micro gravure coating method, and a gravure coating method. , Bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, ink jet printing method and the like.
- the gate electrode 12, the source electrode 16, and the drain electrode 18 are made of a conductive material.
- conductive materials include metals such as aluminum, gold, platinum, silver, copper, chromium, nickel, and titanium, conductive oxides such as ITO, poly (3,4-ethylenedioxythiophene), and polystyrenesulfone.
- metals such as aluminum, gold, platinum, silver, copper, chromium, nickel, and titanium
- conductive oxides such as ITO, poly (3,4-ethylenedioxythiophene), and polystyrenesulfone.
- examples include conductive polymers such as acid-mixed polymers. It is also possible to use conductive materials in which fine metal particles, carbon black, and graphite fine powder are dispersed in a binder!
- the element substrate 30 having the above-described configuration can be manufactured by a known transistor manufacturing method. For example, a method described in US Pat. No. 6,107,117 can be applied.
- the semiconductor film 22 to be the active layer 20 may be composed of only an organic semiconductor compound or may further contain additional components other than the organic semiconductor compound.
- the organic semiconductor compound include a low molecular organic semiconductor compound and a high molecular organic semiconductor compound.
- the additive component include a dopant, an adjustment material for adjusting carriers in the active layer 20, and a polymer material for enhancing the mechanical properties of the semiconductor film.
- the semiconductor film 22 may include a plurality of types of organic semiconductor compounds and a plurality of types of additive components.
- a polymer organic semiconductor compound is more preferable than a low molecular organic semiconductor compound in terms of obtaining a good film forming property.
- Examples of the low-molecular organic semiconductor compound and the high-molecular organic semiconductor compound include compounds exemplified below.
- the organic semiconductor compound contained in the active layer 20 in the transistor of the present invention is not necessarily limited to those exemplified below.
- Examples of the low molecular organic semiconductor compound include anthracene, tetracene, pentacene, benzopentacene, dibenzopentacene, tetrabenzopentacene, naphthopentacene, hexacene, heptacene, nanoacene, and other polyacene compounds; phenanthrene, picene, fluorene, and pyrene.
- derivatives of these low molecular organic semiconductor compounds can also be used.
- An example of this is rubrene, a benzene ring addition derivative of tetracene.
- carbon nanotubes and the like in which a conjugated system of fullerenes is expanded can be exemplified.
- the polymer organic semiconductor compound includes polythiophene, polyphenylene, polyarylene, polyphenylene vinylene, polyphenylene vinylene, polyacetylene, polydiacetylene, polytriphenylamine, triphenylamine, and phenol.
- examples thereof include a copolymer of lembylene, a copolymer of thiophene and phenylene, a copolymer of thiophene and fluorene, and the like.
- derivatives of these high molecular organic semiconductor compounds can also be used. Examples of such include poly (3-hexylthiophene) which is an alkyl-substituted polythiophene.
- polymer organic semiconductor compound examples include those having the following structures.
- RR 2 , R 3 , R 4 , R 5 , R 6 , RR 8 and R 9 are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, or an aryloxy group.
- Group Mono-thio group, arylalkyl group, arylalkylalkoxy group, arylalkylthio group, arylalkyl group, arylalkyl group, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group Represents a monovalent heterocyclic group, a halogen atom or a cyano group.
- n is an integer of 1 or more.
- Examples of the dopant which is an additive component other than the organic semiconductor compound include an acceptor dopant and a donor dopant.
- the acceptor dopant includes halogens such as iodine, bromine, chlorine, iodine chloride, and brominated iodine; sulfur oxide compounds such as sulfuric acid, sulfuric anhydride, sulfur dioxide, and sulfate; nitric acid, nitrogen dioxide, Nitric oxide compounds such as nitrates; Halogenated compounds such as perchloric acid and hypochlorous acid; Acids such as tetrafluoroboric acid, tetrafluoroborate, phosphoric acid, phosphate, and trifluoroacetic acid Or a salt thereof: tetracyanoquinodimethane, tetrachlorotetracyanoquinodimethane, tetrafluorotetracyanodimethane, tetracyanethylene, dichlorocyanoethylene, dichlorodiscyanoquinone, tetrachloroquinone, carbonic acid Examples thereof include gas and oxygen.
- halogens such as io
- donor dopants include tetrathiafulvalene, tetramethyltetrathiafulvalene, tetraselenathiafulvalene; Miny compounds; alkali metals, alkaline earth metals, rare earth metals, complexes of these metals with organic compounds, and the like can be exemplified.
- Other adjustment materials for adjusting the carriers in the active layer 20 include conductive materials such as transition metals such as aluminum, iron, copper, nickel, zinc, silver, platinum, gold, and fine particles thereof. A child.
- polycarbonate polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like are available. Can be mentioned.
- a semiconductor film 22 In the manufacture of such a semiconductor film 22, for example, first, an organic semiconductor compound, or an organic semiconductor compound and other additive components are dissolved and dispersed in an organic solvent to obtain a solution. Next, this solution is applied onto, for example, a polytetrafluoroethylene resin board, and then the organic solvent is volatilized. Thereby, the semiconductor film 22 is obtained. This semiconductor When the body film 22 is used, it is preferable to peel off the semiconductor film 22 from the polytetrafluoroethylene resin board cover.
- Examples of the organic solvent used in the solution for producing the semiconductor film 22 include chlorine-based solvents such as chloroform, methylene chloride, dichloroethane, and trichlorobenzene; ether-based solvents such as tetrahydrofuran; toluene, xylene And aromatic hydrocarbon solvents such as mesitylene, tetralin, decalin and n-butylbenzene; and aromatic solvents having an alkoxy group such as anisole.
- chlorine-based solvents such as chloroform, methylene chloride, dichloroethane, and trichlorobenzene
- ether-based solvents such as tetrahydrofuran
- toluene toluene
- aromatic hydrocarbon solvents such as mesitylene, tetralin, decalin and n-butylbenzene
- aromatic solvents having an alkoxy group such as anisole.
- the solution coating method includes spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, and spray coating. Examples thereof include a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method.
- the obtained semiconductor film 22 is stretched.
- the stretching method of the semiconductor film 22 include methods such as uniaxial stretching, biaxial stretching, swollen stretching in liquid, and stretching using a roll.
- Uniaxial stretching is a method in which a pair of opposite sides of a rectangular semiconductor film 22 is sandwiched between chucks and stretched in the opposite direction. At this time, it may be pulled at room temperature or may be pulled while being heated appropriately. Tensioning can be performed in a specific gas atmosphere such as nitrogen gas.
- biaxial stretching is a method in which two pairs of opposite sides of the semiconductor film 22 having a quadrangular shape are sandwiched between chucks and the film is stretched and stretched in two opposite directions simultaneously or sequentially. At this time, it may be pulled at room temperature or may be pulled while being heated appropriately. The tension can also be performed in a specific gas atmosphere such as nitrogen gas.
- in-swelling stretching means that the semiconductor film 22 is immersed in an appropriate solution that swells without dissolving the semiconductor film 22, and the film is pulled by the above-described uniaxial stretching or biaxial stretching. It is a method of stretching. In this case, pulling should be done while heating at an appropriate temperature.
- the organic semiconductor compound constituting the semiconductor film 22 is aligned in the stretching direction and arranged in a certain method. That is, by the above stretching, the semiconductor film 22 Are oriented in the stretching direction.
- the active layer 20 composed of the semiconductor film 22 oriented in this way has a high carrier mobility. Therefore, the soot transistor 100 having the active layer 22 formed from the stretched semiconductor film 22 (the so-called soot transistor 105, 110, 115, 120, 125 described later) has excellent transistor characteristics in terms of carrier mobility. It will be a thing.
- the stretched semiconductor film 22 is bonded to the insulating layer 14 in the element substrate 30 while performing heating and Z or pressurization.
- a sticking process is performed (Fig. 7 (c)).
- the insulating layer 14 corresponds to a surface on which the surface active layer 20 to which the semiconductor film 22 is attached is formed.
- a specific method of bonding is not particularly limited. For example, first, the semiconductor film 22 is placed on the insulating layer 14 on which the source electrode 16 and the drain electrode 18 are formed. Next, the semiconductor film 22 placed on the insulating layer 14 is adhered to the insulating layer 14 by heating and Z or pressurization.
- the sticking step only one or both of heating and pressing may be performed. Moreover, when performing both, you may make it perform either one after heating and pressurization simultaneously, and the other later. Further, in the pasting step, the pasting may be performed under reduced pressure in order to further improve the adhesion. In addition, when heating or the like is performed in the atmosphere, a preferable characteristic change such as oxidation may occur depending on the type of the organic semiconductor compound. Therefore, the affixing step may be performed under an environment where light, moisture, oxygen, and the like are controlled under reduced pressure, as well as under a nitrogen atmosphere and light shielding, if necessary.
- Suitable heating conditions include a temperature condition that is not lower than room temperature and does not cause deformation of the semiconductor film 22, the insulating layer 14 bonded thereto, the element substrate 30, and the like.
- a temperature condition that is not lower than room temperature and does not cause deformation of the semiconductor film 22, the insulating layer 14 bonded thereto, the element substrate 30, and the like.
- the semiconductor film 22 is made of a polymer organic semiconductor compound, a temperature equal to or lower than the liquid crystal phase or the isotropic phase transition temperature is preferable.
- the semiconductor film 22 also has a low molecular organic compound power, a temperature below its melting point is preferable. It should be noted that even if the temperature exceeds these, it can be carried out if the heating is performed in a short time so as not to cause the above-mentioned disadvantages.
- the pressurization is performed in the stacking direction of the semiconductor film 22 and the insulating layer 14, but for example, the semiconductor film 22 Alternatively, the entire upper surface of the semiconductor film 22 and the element substrate 30 may be pressurized using a roll that may apply a load.
- the pressure during the pressurization is preferably set to a level that does not cause deformation or failure of the semiconductor film 22, the insulating layer 14 constituting the element substrate 30, the substrate 10, the source electrode 16, or the drain electrode 18. ,.
- a working solution may be interposed between the semiconductor film 22 and the insulating layer 14.
- a liquid substance (liquid) having the property of being able to wet both the insulating layer 14 and the semiconductor film 22 is used. Thereby, the semiconductor film 22 and the insulating layer 14 are wetted well, and the adhesion between them can be further improved.
- a contact angle with the surface on which the active layer 20 of the insulating layer 14 is formed is preferably 120 degrees or less, more preferably 90 degrees or less, and 60 degrees is more preferable. What is the force S is more preferable.
- the “contact angle” refers to the tangent drawn in the working liquid from the contact point of these three phases when the liquid droplet of the working liquid is formed on the insulating layer 14 in the air. Of the angles formed with the surface, the angle that contains the working fluid.
- a suitable working solution is appropriately selected according to the type of the insulating layer 14 (contact angle with the insulating layer 14). For example, if the surface of the insulating layer 14 is silicon oxide (SiO, etc.)
- silicon oxide modified with rutiletrichlorosilane octadecyltrichlorosilane, etc.
- silicon nitride organic insulating film, etc.
- methanol, ethanol, C1-C8 alcohol solvent such as isopropanol
- ketone solvent such as acetone
- ether solvent such as jetyl ether
- halogen solvent such as black mouth form (more preferably a mixture of alcohol, etc. )
- Aromatic hydrocarbon solvents such as toluene (more preferably mixed with alcohol), aliphatic hydrocarbon solvents such as hexane, heptane, and octane, water (more preferably containing a surfactant) thing)
- Suitable are -tolyl solvents such as acetonitrile, ester solvents such as ethyl acetate, and solvents containing amine compounds such as aqueous ammonia.
- the application liquid adjusts the concentration of carriers in the active layer 20 and additives such as surfactants for adjusting the wettability to the insulating layer 14, dopants that can adjust the transistor characteristics of the active layer 20, and the like. It may further include a material for the purpose. In addition, said solvent illustrated as a construction liquid may be used independently, and may mix and use 2 or more types. [0077] As a method for interposing the working liquid between the semiconductor film 22 and the insulating layer 14 and bonding them together, for example, the working liquid is formed on one surface of the semiconductor film 22 and the insulating layer 14. After coating, the method of laminating the other on this working solution can be mentioned.
- Other methods include a method in which the semiconductor film 22 and the insulating layer 14 are held with a predetermined gap (gap) and a working solution is injected into the gap. it can.
- the construction liquid has a contact angle of 120 degrees or less with the insulating layer 14 as described above, the surface of the insulating layer 14 can be efficiently wetted, and bonding is further improved. It is possible to do this.
- the construction liquid when used, a removal process for removing unnecessary volatile components in the construction liquid is performed.
- the semiconductor film 22 and the insulating layer 14 are in close contact with each other, and the transistor 100 of the first embodiment is obtained (FIG. 7 (d)).
- the construction liquid may be completely removed or a part of it may remain. For example, if the adhesiveness between the insulating layer 14 and the active layer 20 is kept good, the entire working solution may be removed.
- the thickness of the active layer 20 in the transistor 100 is preferably 10 nm or more, more preferably 40 nm or more, and even more preferably 200 nm or more.
- the thickness of the active layer 20 is 10 ⁇ m or more, sufficiently good transistor characteristics can be obtained.
- by increasing the thickness of the active layer 20 there is a tendency that inconvenience due to physical damage or the like that occurs during manufacturing is less likely to occur.
- the preferred thickness of the active layer is the same in the transistors of the second and third embodiments described below.
- the semiconductor film 22 is stretched and then bonded to the insulating layer 14.
- the transistor manufacturing method of the present invention is not limited to this, and the semiconductor After the film 22 is bonded to the insulating layer 14, the semiconductor film 22 may be stretched. In this case, for example, after the semiconductor film 22 is bonded to the insulating layer 14, the entire laminated substrate 30 to which the semiconductor film 22 is bonded is stretched, so that the semiconductor film 22 after bonding is stretched. It can be carried out. Moreover, you may perform both extending
- the semiconductor film 22 is stretched and then bonded to the insulating layer 14.
- the orientation of the semiconductor film 22 can be appropriately adjusted by stretching the semiconductor film 22 by force.
- factors that inhibit the adhesion of the semiconductor film 22 to the insulating layer 14 and the like by the stretching operation such as distortion of the semiconductor film 22).
- the semiconductor film 22 can be satisfactorily attached to the insulating layer 14.
- orientation of the semiconductor film 22 is caused by the stretching of the semiconductor film 22, but it is not always necessary that the orientation occurs. Oh ,.
- the carrier mobility of the transistor may be improved by factors other than orientation, such as the semiconductor film 22 having a suitable shape by stretching.
- FIG. 8 is a process diagram showing a method for manufacturing a transistor according to the second embodiment.
- an element substrate 32 including a gate electrode 12, an insulating layer 14 formed on the gate electrode 12, and a source electrode 16 and a drain electrode 18 formed on the insulating layer 14 is prepared.
- the gate electrode 12 also functions as a substrate.
- a metal substrate such as highly doped silicon or aluminum is suitable.
- the insulating layer 14 and the source and drain electrodes 16, 18 can be formed in the same manner as in the first embodiment.
- the active layer 20 containing an organic semiconductor compound is to be formed.
- a semiconductor film 22 is prepared (FIG. 8B). Then, the semiconductor film 22 is stretched as in the first embodiment. Then, a pasting step is performed in which the semiconductor film 22 and the insulating layer 14 in the element substrate 32 are pasted together while heating, Z, or pressurizing (FIG. 8C). If a construction liquid is used in this sticking process, a removal process is further performed to remove unnecessary volatile components in the construction liquid as necessary. Thereby, the transistor 105 according to the second embodiment is obtained (FIG. 8D).
- the stretching of the semiconductor film 22 may be performed after pasting before the pasting with the insulating layer 14.
- the entire element substrate 32 to which the semiconductor film 22 is bonded is stretched in a predetermined direction.
- FIG. 9 is a process diagram showing a method for manufacturing a transistor according to the third embodiment.
- a laminate in which the semiconductor film 22 and the support film 52 are bonded together is used as a material for forming the active layer.
- the gate electrode 12, the insulating layer 14 formed on both surfaces of the gate electrode 12, and the source electrode 16 and the drain electrode 18 formed on one insulating layer 14. Is prepared (FIG. 9 (a)).
- a laminated body 50 in which the semiconductor film 22 is laminated on the support film 52 is prepared (FIG. 9 (b)).
- the insulating layer 14, the source electrode 16 and the drain electrode 18 in the element substrate 34 can be formed in the same manner as in the first embodiment.
- the support film 52 in the laminate 50 may be made of either an inorganic material or an organic material.
- an inorganic material for example, polysiloxane, fluorine-based resin, polyethylene, polypropylene, methylpentene resin, polycarbonate, polyimide, polyamide, butyl chloride, vinylidene chloride, acrylic resin, methallyl resin, polystyrene, nylon, polyester, polybutyl alcohol Etc. can be illustrated.
- the support film 52 is preferably one that can handle a predetermined orientation operation.
- a support film 52 for example, polyethylene, polypropylene, methylpentene resin, polycarbonate, polyimide, polyamide, vinyl chloride, polyvinylidene chloride, methacrylic resin, nylon, polyester, polybutyl alcohol and the like are suitable. is there.
- the support film 52 may include a layer having a functionality that promotes peeling from the semiconductor film 22 laminated on the support film 52.
- a layer includes a layer having a function of converting light into heat and a layer that expands by heat. These layers can promote peeling between the support film 52 and the semiconductor film 22 by heat. Therefore, when the support film 52 has these layers, the support film 52 can be easily removed from the active layer 20 by irradiating light or heating after the attaching step of attaching the laminate 50 and the insulating layer 14 together. It becomes possible to peel.
- the support film 52 has a layer having a function of converting light into heat as described above or a layer that expands by heat
- patterning of the active layer 20 may be facilitated. That is, for example, after the laminated body 50 is attached to the insulating layer 14, a predetermined portion of the semiconductor film 22 is irradiated with light through the support film 52 or heated by a trowel. In this way, the light irradiated portion and the heated portion of the semiconductor film are transferred onto the insulating layer 14, while other portions are easily peeled off together with the support film 52. As a result, only the predetermined portion of the semiconductor film 22 remains on the insulating layer 14, thereby forming a patterned active layer 20.
- the laminated body 50 is formed by, for example, bonding the support film 52 and the semiconductor film 22 formed in advance, applying the organic semiconductor compound to the support film 52 directly, or the support film 52. It can be formed by directly applying a solution of the organic semiconductor compound to the substrate. For example, in the case of a solid organic semiconductor compound, the organic semiconductor compound is directly applied to the support film 52 by vapor deposition of the organic semiconductor compound on the support film 52, spray coating of a melt, sublimation application, etc. It can be carried out.
- the direct application of the organic semiconductor compound solution to the support film 52 includes, for example, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, Wire bar coating method, dip coating method, spray coating method, screen Lean printing, flexographic printing, offset printing, inkjet printing, and the like can be used.
- the semiconductor film 22 When the semiconductor film 22 is oriented before being attached to the insulating layer 14, it can be performed in the state of the stacked body 50.
- the orientation can be performed, for example, by uniaxial stretching, biaxial stretching, in-swelling stretching, etc., as in the first embodiment.
- the support film 52 is also stretched together with the semiconductor film 22.
- the semiconductor film 22 may be formed by other methods known as liquid crystal alignment methods.
- the orientation may be performed. Examples of such methods include “Fundamentals and Applications of Liquid Crystals” (Shinichi Matsumoto, Kyoji Kakuda, Industrial Research Society, 1991), Chapter 5, “Structures and Physical Properties of Ferroelectric Liquid Crystals” (Atsuo Fukuda, Co-authored by Hideo Takezoe, Corona Inc., 1990) Chapter 7, “Liquid Crystal”, Vol. 3 No. 1 (1999), pages 3-16, etc. These orientation methods can be performed in place of stretching also in the first and second embodiments described above and in the fourth to sixth embodiments described later.
- an alignment method for example, a rubbing method, a photo-alignment method, a shearing method (shear stress application method) and a pulling coating method are simple and useful and particularly easy to use.
- the rubbing method is a method in which the support film 52 is lightly rubbed with a cloth or the like.
- cloth such as gauze, polyester, cotton, nylon and rayon can be used.
- the cloth used for rubbing can be appropriately selected according to the film to be oriented. In this case, if an alignment film is separately formed on the support film 52, the alignment performance becomes higher.
- the alignment film include polyimide, polyamide, polybutyl alcohol, polyester, nylon, and the like, and a commercially available alignment film for liquid crystal is also applicable.
- the alignment film can be formed by spin coating or flexographic printing.
- the photo-alignment method is a method of providing an alignment function by forming an alignment film on the support film 52 and irradiating polarized UV light or obliquely irradiating UV light.
- the alignment film include polyimide, polyamide, and polyvinyl cinnamate. Commercially available alignment films for liquid crystals can also be applied.
- the organic semiconductor compound (semiconductor film 22) laminated on the support film 52 subjected to the above treatment can be oriented by such a rubbing method or an optical orientation method. This orientation is This is caused by allowing the organic semiconductor compound to have a liquid crystal phase or isotropic phase temperature on the support film 52.
- the semiconductor film 22 formed on the support film 52 can also be oriented by applying the organic semiconductor compound onto the support film 52 after the alignment treatment.
- the organic semiconductor compound when an organic semiconductor compound is applied on the support film 52, the organic semiconductor compound is applied on the support film 52, and the liquid crystal phase or the isotropic phase is exhibited.
- the orientation can be generated by setting the temperature at such a temperature and coating in one direction with a rod or the like.
- a solution in which the organic semiconductor compound is dissolved in an organic solvent may be prepared and applied by spin coating or flexographic printing. Even if the organic semiconductor compound does not have liquid crystallinity, the organic semiconductor compound can be deposited on the orientation-supported support film 52 as long as it can be deposited.
- a layer (semiconductor film 22) made of an oriented organic semiconductor compound can be obtained by vapor deposition in an epitaxy manner.
- the sharing method is a method in which another substrate is placed on the organic semiconductor composite placed on the support film 52, and the organic semiconductor composite is at a temperature at which it becomes a liquid crystal phase or an isotropic phase.
- the upper substrate is shifted in one direction.
- the semiconductor film 22 having a higher degree of alignment can be obtained.
- the upper substrate include glass and polymer film, and may be a metal rod or the like.
- the lift coating method is to form an oriented organic semiconductor compound layer (semiconductor film 22) on the support film 52 by immersing the support film 52 in an organic semiconductor compound solution and pulling it up. Is the method. Conditions such as the organic solvent used in the organic semiconductor compound solution and the pulling speed of the support film 52 are not particularly limited, but it is preferable to select and adjust according to the desired degree of orientation of the organic semiconductor compound.
- the laminated body 50 and the element substrate 34 A pasting process is performed in which the insulating layer 14 is bonded to the insulating layer 14 while heating and applying Z or pressure (Fig. 9 (c)).
- the heating and pressurizing conditions can be the same as those in the first embodiment.
- the pasting process may be performed under reduced pressure conditions to further improve adhesion and further promote removal of the construction liquid!
- the transistor 110 of the third embodiment in which the support film 52 is laminated on the active layer 20 is obtained (FIG. 9 (d)). Note that after the transistor 110 is completed, the support film 52 may be removed. If there is no practical problem, the support film 52 may be laminated as it is. When the support film 52 is laminated, the support film 52 also has a function capable of protecting against factors that deteriorate the characteristics of the active layer 20 (physical damage, influence of gas by the atmosphere, charging, etc.). Is preferably applied.
- either the step of orienting the semiconductor film 22 and the attaching step may be performed first as described above.
- the step is performed first. After the semiconductor film 22 is oriented, it is preferable to perform a pasting process using the oriented semiconductor film 22. By doing so, the active layer 20 having a desired orientation tends to be more easily obtained.
- FIG. 10 is a process diagram showing a method for manufacturing a transistor according to the fourth embodiment.
- a first element substrate 36 including a gate electrode 12 and an insulating layer 14 formed thereon is prepared (FIG. 10 (a)).
- the gate electrode 12 also has a function as a substrate.
- the configuration and manufacturing method of the gate electrode 12 and the insulating layer 14 can be performed in the same manner as in the second embodiment.
- a semiconductor film 22 to be the active layer 20 containing an organic semiconductor compound is prepared (FIG. 10 (b)). Subsequently, stretching of the semiconductor film 22 and other treatments for imparting orientation are performed as appropriate. Then, the semiconductor film 22 and the insulating layer 14 in the first element substrate 36 are bonded together by heating and applying Z or pressure. Perform the process (Fig. 10 (c)). Thus, the second element substrate 60 in which the active layer 20 is formed on the element substrate 36 is formed (FIG. 10D). In this pasting step, a laminated body 50 as in the third embodiment may be used instead of the semiconductor film 22. In this case, after pasting, the support film 52 in the laminated body 50 is removed, and the following operation is performed for the force.
- the source electrode 16 and the drain electrode 18 are formed on the active layer 20 in the second element substrate 60 in the same manner as in the first embodiment or the like, thereby the transistor 115 according to the fourth embodiment. (Fig. 10 (e)).
- the stretching of the semiconductor film 22 and other alignment operations may be performed before or after the semiconductor film 22 is bonded.
- FIG. 11 and FIG. 12 are process diagrams showing a method for manufacturing a transistor according to the fifth embodiment.
- a first element substrate 38 including a substrate 10 and a source electrode 16 formed thereon is prepared (FIG. 11 (a)).
- a semiconductor film 22 to be the active layer 20 containing an organic semiconductor compound is prepared (FIG. 11 (b)), and the semiconductor film 22 is subjected to stretching and other orientation operations. Do. Then, a first pasting step is performed in which the semiconductor film 22 and the source electrode 16 in the first element substrate 38 are pasted together while heating and Z or pressurizing (FIG. 11 (c)). Such a first attaching step can be performed in the same manner as in the first embodiment. Then, the semiconductor film 22 is brought into close contact with the first element substrate 38, and an active layer 20 is formed from the semiconductor film 22 (FIG. 11 (d)) G
- a plurality (four in this case) of gate electrodes 12 are formed on the active layer 20 formed on the first element substrate 38, thereby obtaining the second element substrate 62 ( Figure 11 (e)).
- the same gate electrode 12 as in the first embodiment can be applied.
- a semiconductor film 26 to be the active layer 24 containing the organic semiconductor compound is separately prepared (Fig. 12 (f)).
- the semiconductor film 26 is also subjected to stretching and other orientation operations as appropriate.
- a second pasting step is performed in which the semiconductor film 26 and the active layer 20 in the second multilayer substrate 62 are pasted together while being heated and Z or pressed (FIG. 12 (g)).
- the semiconductor film 26 is attached on the active layer 20 so as to cover the gate electrode 12.
- This second sticking step can also be performed in the same manner as in the first embodiment.
- the construction liquid can be used in the same way as in the above-described embodiment, but the same construction liquid can be used for these processes. May be.
- the semiconductor film 26 is brought into close contact with the active layer 20 so as to sandwich the gate electrode 12, thereby forming the active layer 24 (FIG. 12 (h)).
- the drain electrode 18 is formed in the same manner as in the first embodiment and the like, thereby obtaining the transistor 120 according to the fifth embodiment (FIG. 12 (i)).
- either one of the active layers 20 and 24 may be formed by a method as described in, for example, Japanese Patent Application Laid-Open No. 2004-006476.
- the laminated body 50 as in the third embodiment may be used instead of the semiconductor film 22. In this case, after sticking, the support film 52 in the laminated body 50 is removed, and the force is further operated thereafter.
- the force for performing an orientation operation such as stretching on both of the semiconductor films 22 and 26 for forming the active layers 20 and 24 is not limited to this. If the semiconductor film is subjected to a treatment such as stretching, the carrier mobility can be improved. Further, in this embodiment, after each of the unstretched semiconductor films 22 and 26 is pasted in each pasting step, the board after pasting them (for example, the first element substrate 38 or the second element) An orientation operation such as stretching may be performed on the substrate 62). Furthermore, one semiconductor film should be pasted before stretching, and the other semiconductor film should be pasted after stretching.
- FIG. 13 and 14 are process diagrams showing a method for manufacturing a transistor according to the sixth embodiment.
- this manufacturing method first, a substrate 10 and a source electrode 16 and a drain electrode are formed on the substrate 10.
- An element substrate 64 having a pole 18 is prepared (FIG. 13 (a)).
- the source electrode 16 and the drain electrode 18 can be formed by the same method as in the first embodiment.
- a semiconductor film 22 to be the active layer 20 containing an organic semiconductor compound is prepared (FIG. 13 (b)). Subsequently, the semiconductor film 22 is appropriately subjected to stretching and other operations for imparting orientation as described above. Then, a pasting process is performed in which the stretched or oriented semiconductor film 22 and the substrate 10 in the element substrate 64 are bonded together while heating, Z, or pressurizing (FIG. 13 (c)). As a result, the active layer 20 is formed on the substrate 10 so as to cover the source electrode 16 and the drain electrode 18 (FIG. 13 (d)).
- an insulating layer 14 is formed on the active layer 20 in the same manner as in the first embodiment and the like (FIG. 14 (e)).
- the gate electrode 12 is formed in the same manner as in the first embodiment, thereby obtaining the transistor 125 according to the sixth embodiment (FIG. 14 (f)).
- the laminated body 50 as in the third embodiment can be used in place of the semiconductor film 22 in the attaching step. In this case, the operation of removing the support film 52 from the laminated body 50 and continuing the force after the pasting is performed. Further, when the support film 52 has a function as the insulating layer 14, the insulating film 14 may be used as it is without removing the support film 52.
- the power of explaining the transistor and its manufacturing method of the first to sixth embodiments is not limited to the form, and may be changed as appropriate.
- the active layer 20 (the active layers 20 and 24 in the fifth embodiment) in the transistor of each embodiment is composed of a plurality of layers that need not be a single layer. May be.
- the plurality of layers may be composed of the same material force or different material forces.
- the active layers 20 and 24 composed of a plurality of layers are formed on the semiconductor films 22 and 26 for forming the active layers 20 and 24, after removing the supporting film and the like remaining thereon as necessary. Can be formed by further stacking the same or different types of semiconductor films it can.
- the force in which the source electrode 16 and the drain electrode 18 are in direct contact with the active layer 20 or 24 is not limited to this.
- a layer made of a compound different from the organic semiconductor compound may be interposed between the drain electrode 18 and the active layers 20 and 24.
- the contact resistance between the source electrode 16 and drain electrode 18 and the active layers 20 and 24 is reduced, and the carrier mobility of the transistor can be further improved.
- the compound different from the organic semiconductor compound include a donor compound, an acceptor compound, and a compound having a thiol group.
- the donor compound tetrathiafulvalene, tetramethyltetrathiafluolene, tetraselenathiafulvalene; diphenylphenylenediamine, tetraphenylphenylenediamine, tetraphenyldiaminodiphenyl, polyvinylcarbazole, and other amine compounds And alkali metals, alkaline earth metals, rare earth metals, and complexes of these metals with organic compounds.
- the acceptor compounds include halogens such as iodine, bromine, chlorine, iodine chloride, and brominated iodine; sulfur oxide compounds such as sulfuric acid, anhydrous sulfuric acid, sulfur dioxide, and sulfate; nitric acid, nitrogen dioxide, Nitric oxide anhydrides such as nitrates; Halogenated compounds such as perchloric acid and hypochlorous acid; Acids such as tetrafluoroboric acid, tetrafluoroborate, phosphoric acid, phosphate, trifluoroacetic acid or Its salts; tetracyanoquinodimethane, tetrachlorotetracyanodimethane, tetrafluorotetracyanodimethane, tetracyanethylene, dichlorocyanoethylene, dichlorodiscyanoquinone, tetrachloroquinone, etc. .
- halogens such as iodine, bromine, chlorine
- examples of the compound having a thiol group include alkyl thiols, alkyl thiols such as fluorinated alkyl thiols, aromatic thiols, fluorinated alkyl aromatic thiols, fluorinated aromatic thiols, nitro Aromatic thiol compounds such as aromatic thiols and amino aromatic thiols.
- the layer having the compound force is formed, for example, by bringing a solution or gas of the compound into contact with the surface of the source electrode 16 or the drain electrode 18 and adsorbing the compound onto the contact surface. Can do.
- the thicknesses of the source electrode 16 and the drain electrode 18 are not particularly limited. However, when the active layers 20 and 24 are formed on the source electrode 16 and the drain electrode 18 as in the first to third and fifth embodiments, the adhesion with the active layers 20 and 24 is further increased. In order to be good, the source electrode 16 and the drain electrode 18 are as thin as possible without losing their function as electrodes! I like it.
- the transistors of the first to sixth embodiments can be sealed after completion of the above-described element configuration to be sealed transistors.
- the transistor is shielded from atmospheric forces and is also protected from physical damage and the like, and it is possible to suppress degradation of transistor characteristics.
- the element configuration is covered with an insulating polymer, UV-cured resin, heat-cured resin, or an organic acid-silicon film or silicon nitride film.
- an insulating polymer for example, UV-cured resin, heat-cured resin, or an organic acid-silicon film or silicon nitride film.
- a method of bonding a glass plate or a film with a UV-cured resin or a heat-cured resin can be used.
- the process from the creation of the transistor to the sealing is performed without exposure to the atmosphere (for example, in a dry nitrogen atmosphere and stored in a vacuum). Is preferred.
- the above-described transistor is preferably applied to a semiconductor device.
- semiconductor devices include wireless tags, displays, and large sensors.
- a logic circuit can be formed by using, for example, transistors alone or in combination with a plurality of other transistors. Specifically, it is suitable as a switching transistor, a signal driver circuit element, a memory circuit element, a signal processing circuit element, or the like of a pixel of a display which is a semiconductor device.
- the display can be widely applied to electronic paper, liquid crystal or organic LED.
- Poly (3-hexylthiophene) and poly (3-octylthiophene) purchased from Aldrich were used. These poly (3-hexylthiophene) and poly (3- Octinoretiophene) was regioregular.
- the surface of a heavily doped n-type silicon substrate 201 to be a gate electrode also serving as a substrate is thermally oxidized to form an insulating layer made of a silicon oxide film.
- 203 was formed at 2 OOnm, and this was used as a support substrate.
- gold is vapor-deposited on the surface of one insulating layer 203 of the substrate 201 to a thickness of 65 nm by a vacuum vapor deposition method.
- a source electrode 204a and a drain electrode 204b are formed.
- the electrode channel width was 500 ⁇ m and the channel length was 20 ⁇ m.
- the surface of the insulating layer 203 is coated with an octane solution of octyltrichlorosilane ( The element substrate 206 was formed by soaking in 6 mmol Zl).
- a laminate for forming an active layer was prepared separately from the element substrate 206. That is, first, a closed mouth form solution (2.0 wt%) of poly (3-hexylthiophene) was prepared in the atmosphere.
- a poly (3-hexylthiophene) black mouthform solution was placed on the polyethylene film as the support film 207. It apply
- a laminate 205 in which the poly (3-hexylthiophene) film 208 was laminated on the polyethylene support film 2007 was formed.
- this laminate 205 was uniaxially stretched 2.5 times at 100 ° C under a nitrogen atmosphere.
- a stretched laminate 215 having a stretched support film 217 and a stretched poly (3-hexylthiophene) film 218 was obtained (FIG. 15 (d)).
- the orientation state of the poly (3-hexylthiophene) film 218 in the stretched laminate 215 was confirmed as follows. That is, first, a part of the stretched laminate 215 was cut out and pressure-bonded to a slide glass heated to 60 ° C. on a hot plate so that the surface of the poly (3-hexylthiophene) film 218 was in contact.
- the poly (3-hexylthiophene) film 218 was transferred to a slide glass by peeling only the support film 217 with tweezers. This transferred poly (3-hexylthiophene) film 218 was observed with a polarizing microscope. As a result, it was confirmed that the poly (3 hexylthiophene) film 218 was oriented in the stretching direction of the laminate 205 described above.
- the stretched laminated body 215 is formed on the insulating layer 203 on which the source electrode 204a and the drain electrode 204b are formed, and the poly (3-hexylthiophene) film 218 force. Tweezers were placed so as to face the insulating layer 203 on which the source electrode 204a and the drain electrode 204b were formed. Furthermore, the surface of the stretched laminate 215 was rubbed very softly with Bencoton (Asahi Kasei) from above. At this time, the extending direction of the extending laminate 215 was made parallel to the direction connecting the source electrode 204a and the drain electrode 204b.
- a silicon substrate 201 was used as a gate electrode, and a gate voltage V of +50 to 1-40 V and a source-drain voltage V of 140 V were applied in a nitrogen atmosphere to obtain a transistor.
- the transistor characteristics were measured. As a result, the mobility obtained by the IV characteristics is 1.7 X 10 cm ZVs.
- Example 1 as in Example 1 except that heating at 45 ° C for 45 minutes 2 transistors 200 were obtained.
- a silicon substrate 201 was used as a gate electrode, and a gate voltage V of +50 to 1-40 V and a source-drain voltage V of 140 V were applied in a nitrogen atmosphere to obtain a transistor.
- the transistor characteristics were measured. As a result, the mobility obtained from the IV characteristics was 2.8 X 10 cm ZVs.
- Example 3 In the production of the transistor of (3), after the stretched laminate 215 was placed on the element substrate 206, only the operation of applying a load of 2.7 kg / cm 2 for 30 minutes in a nitrogen atmosphere was performed. Then, a transistor 200 of Example 3 was obtained in the same manner as Example 1.
- a silicon substrate 201 was used as a gate electrode, and a gate voltage V of +50 to 1-40 V and a source-drain voltage V of 140 V were applied in a nitrogen atmosphere to obtain a transistor.
- a transistor 200 of Comparative Example 1 was obtained in the same manner as Example 1 except that in the production of the transistor of (3), the element substrate 206 on which the stretched laminate 215 was placed was not heated.
- a silicon substrate 201 was used as a gate electrode, and a gate voltage V of +50 to 1-40 V and a source-drain voltage V of 140 V were applied in a nitrogen atmosphere to obtain a transistor.
- the transistor characteristics were measured. As a result, the mobility obtained from the IV characteristics was 2.0 x 10 cm ZVs.
- a stacked body for forming an active layer was prepared as shown in FIG. 15 (c). That is, first, a poly (3-hexylthiophene) chloroform solution (2. Owt%) was prepared in the atmosphere.
- a stacked body 205 is formed on the insulating layer 203 on which the source electrode 204a and the drain electrode 204b are formed, and the poly (3-hexylthiophene) film 20 8 force. Tweezers were placed so as to face the insulating layer 203 on which the source electrode 204a and the drain electrode 204b were formed. Furthermore, the surface of the laminate 205 was rubbed very softly with Ben Cotton (Asahi Kasei) from above.
- the element substrate 206 on which the laminate 205 was placed was heated at 80 ° C for 40 minutes in a nitrogen atmosphere using a hot plate.
- a transistor 210 of Comparative Example 2 including an unextended active layer 228 made of poly (3 hexylthiophene) was obtained (FIG. 16 (b)).
- a silicon substrate 201 was used as a gate electrode, and a gate voltage V of +50 to 1-40 V and a source-drain voltage V of 140 V were applied in a nitrogen atmosphere to obtain a transistor.
- the transistor characteristics were measured. As a result, the mobility obtained by the IV characteristics is 1.1 x 10 cm ZVs.
- a silicon substrate 201 is used as a gate electrode, a gate voltage V of +40 to 40 V and a source-drain voltage V of 140 V are applied in a nitrogen atmosphere, and a transistor is applied.
- the transistor characteristics were measured. As a result, mobility obtained the I-V characteristic mosquito ⁇ et is 2. was 0 X 10 cm ZVs der Q
- a silicon substrate 201 was used as a gate electrode, and a gate voltage V of +50 to 140 and a source-drain voltage V of 140 V were applied in a nitrogen atmosphere.
- the layer 500 of 4 (trifluoromethyl) thiophenol was formed by immersing the element substrate 206 in an ethanol solution (ImmolZL) of 4- (trifluoromethyl) thiophenol for 0.5 hour.
- a silicon substrate 201 is used as a gate electrode, a gate voltage V of +40 to 40 V and a source-drain voltage V of 140 V are applied in a nitrogen atmosphere, and a transistor is applied.
- a transistor was obtained in the same manner as in Example 4 except that the unstretched laminate 205 similar to Comparative Example 2 was used instead of the stretched laminate 215. Thereby, instead of the active layer 220 and the stretched support film 217, the configuration similar to that of the transistor 300 of Example 4 is provided except that the active layer 220 and the unstretched support film 207 are respectively provided. A transistor of Comparative Example 6 was obtained.
- a silicon substrate 201 is used as a gate electrode, a gate voltage V of +40 to 40 V and a source-drain voltage V of 140 V are applied in a nitrogen atmosphere, and a transistor is applied.
- the transistor characteristics were measured. As a result, the mobility obtained from the IV characteristics is 2.7 X 10 cm ZVs.
- the 4 (trifluoromethyl) thiophenol layer 500 was formed on the source electrode 204a and the drain electrode 204b in the same manner as in Example 4. Further, an element substrate 216 (FIG. 18) was obtained.
- a droplet of methanol is placed as a working liquid 9 with a spoid, and the stretched laminate 215 is placed through the working liquid 9 with the stretched laminate 215.
- the poly (3 hexylthiophene) film 218 was placed with tweezers so as to face the insulating layer 203 on which the source electrode 204a and the drain electrode 204b were formed.
- the extending direction of the extending laminate 215 was set to be parallel to the direction connecting the source electrode 204a and the drain electrode 204b. And it left still until the methanol which is the construction liquid 9 was dried and removed.
- the stretched laminate 215 was naturally adhered onto the insulating layer 203 so as to cover the source electrode 204a and the drain electrode 204b.
- a heat treatment at 80 ° C. for 40 minutes was performed in the same manner as in Example 4.
- the transistor of Example 5 having the same configuration as that of the transistor 300 of Example 4 was obtained.
- a silicon substrate 201 is used as a gate electrode, a gate voltage V of +40 to 40 V and a source-drain voltage V of 140 V are applied in a nitrogen atmosphere, and a transistor is applied.
- the transistor characteristics were measured. As a result, the mobility obtained by the IV characteristics is 1.2 X 10 cm ZVs, which is 7 pieces.
- a silicon substrate 201 is used as a gate electrode, a gate voltage V of +40 to 40 V and a source-drain voltage V of 140 V are applied in a nitrogen atmosphere, and a transistor is applied.
- Table 1 and Table 2 collectively show the characteristics of the transistors obtained in Examples 1 to 5 and Comparative Examples 1 to 7.
- Table 1 shows the characteristics obtained in the transistors of Examples 1 to 5 and Comparative Example 1 obtained by stretching the semiconductor film on which the active layer is to be formed.
- Table 2 shows the semiconductor film. The characteristics obtained with the transistors of Comparative Examples 2 to 7 without stretching were shown.
- the mobility improvement rate values are all heated and pressurized during the formation of the active layer.
- This value is calculated assuming that the mobility of the transistor obtained in the case of trapping is 100%, and indicates the rate of improvement in mobility due to heating and Z or pressurization.
- the transistors of Examples 1 to 5 that were oriented by stretching the semiconductor film forming the active layer were obtained by performing heating and Z or pressurization during the formation of the active layer. As a result, it was confirmed that the transistor has excellent transistor characteristics.
- Example 2 and Comparative Example 3 Example 3 and Comparative Example 4
- stretching was performed. It was found that excellent transistor characteristics with higher mobility than that of the comparative example, which was not stretched, could be exhibited. Furthermore, from comparison between Comparative Example 1 and Comparative Example 5, it was confirmed that the mobility alone was not improved by stretching alone as in the case of combining heating and pressurization. Furthermore, a layer of 4 (trifluoromethyl) thiophenol is provided between the source and drain electrodes and the active layer as in Example 4, or bonding using a working solution is performed as in Example 5. As a result, the mobility was further improved. From comparison with Comparative Examples 6 and 7, it was found that when the active layer was stretched, the above-described effect was remarkably improved as compared with the case where it was not stretched.
- a gate voltage V of +40 to 140 V and a source-drain voltage V of 140 V were applied under a nitrogen atmosphere using the silicon substrate 201 as a gate electrode.
- the transistor characteristics were measured, and the mobility was calculated from the IV characteristics obtained.
- the obtained results are shown in Table 3 together with the film thickness of the active layer 220 in the transistor of each example.
Abstract
Description
Claims
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US12/065,004 US8247264B2 (en) | 2005-08-31 | 2006-08-30 | Transistor, method for manufacturing same, and semiconductor device comprising such transistor |
CN2006800318291A CN101253609B (zh) | 2005-08-31 | 2006-08-30 | 晶体管及其制造方法、以及具有该晶体管的半导体装置 |
GB0804217A GB2445487B (en) | 2005-08-31 | 2006-08-30 | Transistor, method for manufacturing same, and semiconductor device comprising such transistor |
DE112006002267T DE112006002267T5 (de) | 2005-08-31 | 2006-08-30 | Transistor, Verfahren zu seiner Herstellung und Halbleiterbauelement mit einem solchen Transistor |
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EP2175481A1 (en) * | 2007-07-10 | 2010-04-14 | Sumitomo Chemical Company, Limited | Process for producing organic semiconductor element, organic semiconductor element, and organic semiconductor device |
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WO2014072873A1 (en) * | 2012-11-06 | 2014-05-15 | Empire Technology Development Llc | Bi-polar organic semiconductors for thermoelectric power generation |
US9882109B2 (en) | 2012-11-06 | 2018-01-30 | Empire Technology Development Llc | Bi-polar organic semiconductors for thermoelectric power generation |
JP6809223B2 (ja) * | 2015-04-01 | 2021-01-06 | 東レ株式会社 | 整流素子、その製造方法および無線通信装置 |
DE102016104254A1 (de) * | 2016-03-09 | 2017-10-26 | Friedrich-Schiller-Universität Jena | Verfahren zur Herstellung einer halbleitenden Folie und elektronisches Bauelement |
US20180240861A1 (en) * | 2017-02-23 | 2018-08-23 | International Business Machines Corporation | Multilayer dielectric for metal-insulator-metal capacitor (mimcap) capacitance and leakage improvement |
US20220045274A1 (en) * | 2020-08-06 | 2022-02-10 | Facebook Technologies Llc | Ofets having organic semiconductor layer with high carrier mobility and in situ isolation |
CN113540352B (zh) * | 2021-06-18 | 2023-05-23 | 吉林大学 | 溶液加工与真空蒸镀结合制备有机晶体薄膜的方法 |
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- 2006-08-30 CN CN2006800318291A patent/CN101253609B/zh not_active Expired - Fee Related
- 2006-08-30 GB GB0804217A patent/GB2445487B/en not_active Expired - Fee Related
- 2006-08-30 US US12/065,004 patent/US8247264B2/en not_active Expired - Fee Related
- 2006-08-30 DE DE112006002267T patent/DE112006002267T5/de not_active Withdrawn
- 2006-08-30 WO PCT/JP2006/317133 patent/WO2007026781A1/ja active Application Filing
- 2006-08-30 KR KR1020087004754A patent/KR20080047542A/ko not_active Application Discontinuation
- 2006-08-31 TW TW095132228A patent/TWI416633B/zh not_active IP Right Cessation
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EP2175481A4 (en) * | 2007-07-10 | 2013-09-04 | Sumitomo Chemical Co | PROCESS FOR MANUFACTURING AN ORGANIC SEMICONDUCTOR ELEMENT, ORGANIC SEMICONDUCTOR ELEMENT AND ORGANIC SEMICONDUCTOR EQUIPMENT |
Also Published As
Publication number | Publication date |
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GB0804217D0 (en) | 2008-04-23 |
DE112006002267T5 (de) | 2008-07-17 |
KR20080047542A (ko) | 2008-05-29 |
TW200729351A (en) | 2007-08-01 |
GB2445487A (en) | 2008-07-09 |
TWI416633B (zh) | 2013-11-21 |
US8247264B2 (en) | 2012-08-21 |
US20090267055A1 (en) | 2009-10-29 |
GB2445487B (en) | 2011-11-02 |
CN101253609B (zh) | 2012-06-13 |
CN101253609A (zh) | 2008-08-27 |
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