JP2010129742A - Electronic device and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electronic device which can be manufactured by application process (printing and IJ), which does not have abnormal electric discharge by electromagnetic wave irradiation, which has high production efficiency and production stability, and which improves carrier mobility and on/off ratio, and the method of manufacturing the same. <P>SOLUTION: There is provided the method of manufacturing an electronic device which converts a thermal conversion material into a function material using heat generated by a substance having an ability to absorb an electromagnetic wave by having an electrode on a substrate, arranging a thermal conversion material or an area including the thermal conversion material and the substance which is adjacent to or close to the thermal conversion material or the area including the thermal conversion material and which has the ability to absorb the electromagnetic wave or an area including the substance having the ability to absorb the electromagnetic wave on a portion at least, and performing irradiation with the electromagnetic wave. In the method of manufacturing the electronic device, all angles formed by the side of the electrode are larger than 90° and smaller than 180° or are curved surfaces. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electronic device manufacturing method for forming various functional films such as an electrode, an insulating layer, and a semiconductor layer using a substance having an electromagnetic wave absorbing ability, and an electronic device obtained by the manufacturing method. A manufacturing method of an electronic device that can be manufactured by a process (printing or IJ), has no abnormal discharge due to electromagnetic wave irradiation, and can simultaneously form an electrode and a semiconductor forming process, and has high production efficiency and stability. The present invention relates to an electronic device obtained by a manufacturing method.

  Along with the rapid miniaturization of information terminals in recent years, the wiring pitch of the printed wiring board mounted on the information terminal has also been reduced. Specifically, it is formed on the printed wiring board as the circuit in the semiconductor becomes finer. The minimum line width and film thickness of circuit patterns are becoming increasingly narrower.

  Under such circumstances, Japanese Patent Application Laid-Open No. 2002-324966 discloses pattern printing of ultrafine metal particles having an average particle diameter of several nanometers to several hundred nanometers on a substrate by an inkjet method, and the circuit pattern is heated to a temperature of 200 ° C. or higher. Discloses a method of obtaining a conductive circuit pattern by baking.

  Japanese Patent Laid-Open No. 2006-32326 discloses a solution in which ultrafine metal particles having an average particle diameter of 1 to 40 nm are dispersed in a solvent, and a uniform coating film is formed on a substrate by spin coating or spray coating, followed by baking at 400 to 900 ° C. Thus, a method for obtaining a thin film electrode and a thin film element (for example, a dielectric element) is disclosed.

  However, although these methods are firing at a relatively low temperature, if a plastic substrate having a low glass transition temperature and a low melting temperature is used, firing at a lower temperature is required. Element characteristics could not be obtained.

  Japanese Patent Application Laid-Open No. 2004-55363 discloses a colloidal dispersion containing specific metal compound nanoparticles having an average particle diameter of 1 to 20 nm as a method for obtaining a thin film conductive layer on such a substrate having low heat resistance. A method of drawing by an ink jet method and baking using any laser selected from infrared light and ultraviolet light is disclosed.

  This method is an effective method for a substrate having low heat resistance. However, since a laser having a beam diameter of 10 to several tens of μm is scanned, it takes a long time to fire an actually patterned electrode. In other words, there is a description about a transparent conductive film made of a metal oxide, but the detailed description about firing in a fine metal pattern is that the surface resistance is reduced to only about several hundred Ω / □. Has not been.

  Japanese Patent Application Laid-Open No. 2005-294053 also discloses a baking method using microwaves, and this method has a thermal degradability and particles that absorb high-frequency electromagnetic waves on various substrates. After application, high-frequency electromagnetic wave irradiation is performed, whereby the thermally decomposable particles are selectively heated, decomposed, and fused to obtain a low-resistance metal pattern.

  And since the particle | grains which absorb a high frequency electromagnetic wave itself decompose | disassemble and become a metal, there exists an advantage which electromagnetic wave absorption capability lose | disappears and a heating is complete | finished spontaneously.

  However, in order to efficiently produce a conductive pattern by this method, it is necessary to select a material having both high electromagnetic wave absorption capability (dielectric loss) and low decomposition temperature. The efficiency is low unless silver oxide, silver nitride, and silver halide having low temperature decomposition (reduction reaction) properties are used, and it is difficult to obtain a practical conductivity unless silver oxide having high dielectric loss is used.

  On the other hand, it has been pointed out that a discharge phenomenon occurs at the time of microwave irradiation, resulting in thermal runaway at a portion where microwave irradiation is performed, and a crack is generated at the irradiated portion.

  On the other hand, for example, a conductive foam sheet is laid under the coating to prevent discharge during electromagnetic wave irradiation (see, for example, Patent Document 1), and the surface of the transparent conductive film is oxidized. A titanium oxide particle aggregate thin film is applied by applying a titanium fine particle paste, placed on the conductor in such a position that the titanium oxide particle aggregate thin film side is down, and is irradiated with microwaves to discharge. There is a technique for preventing (see, for example, Patent Document 2).

  However, for the purpose of grounding the discharge from the conductive thin film precursors described in Patent Documents 1 and 2, it is necessary to bring the conductor into direct contact with the conductive thin film precursor. There was a problem that it was discharged.

  Furthermore, a technique is disclosed in which discharge is prevented by adjusting the output according to the loss coefficient of an object to be irradiated with microwaves (see, for example, Patent Document 3).

However, when the temperature is raised to a high temperature, the output of the microwave may not be increased, and there is a problem that the formation of the conductive layer that requires a high temperature cannot be raised to a predetermined temperature only by adjusting the output.
JP 2001-91126 A JP 2006-60064 A JP 2001-54730 A

  The object of the present invention is that it can be manufactured by a coating process (printing or IJ), has no abnormal discharge due to electromagnetic wave irradiation, and at the same time has high production efficiency and production stability that enables one step of electrode formation and semiconductor formation steps. Another object of the present invention is to provide an electronic device manufacturing method with improved carrier mobility and on / off ratio and an electronic device obtained by the manufacturing method.

  The above object of the present invention is achieved by the following means.

  1. An area having an electrode on a substrate and containing heat conversion material or heat conversion material in at least one part, and a substance or electromagnetic wave having electromagnetic wave absorption ability adjacent to or adjacent to the heat conversion material or area containing heat conversion material In the method of manufacturing an electronic device in which an area including an absorptive substance is disposed, irradiated with an electromagnetic wave, and heat conversion material is converted into a functional material by heat generated by the electromagnetic wave absorptive substance, A method for manufacturing an electronic device, characterized in that all the angles formed by the sides are larger than 90 ° and smaller than 180 °, or a curved surface.

  2. 2. The method of manufacturing an electronic device according to 1 above, wherein the substance having electromagnetic wave absorbing ability is a metal oxide.

  3. 3. The method of manufacturing an electronic device according to 1 or 2, wherein the substance having the ability to absorb electromagnetic waves is a conductor.

  4). 4. The method of manufacturing an electronic device according to 2 or 3, wherein the metal oxide includes at least one of In, Sn, and Zn.

  5. 5. The electronic device manufacturing method according to any one of 1 to 4, wherein the electronic device is a transistor element.

  6). 6. The method for manufacturing an electronic device according to any one of 1 to 5, wherein the heat conversion material is a semiconductor precursor material.

  7). 6. The method of manufacturing an electronic device according to any one of 1 to 5, wherein the heat conversion material is an insulating film precursor material.

  8). 6. The method of manufacturing an electronic device according to any one of 1 to 5, wherein the heat conversion material is a protective film precursor material.

  9. 6. The method for manufacturing an electronic device according to any one of 1 to 5, wherein the heat conversion material is an electrode precursor material.

  10. 10. The method of manufacturing an electronic device as described in 9 above, wherein the electrode precursor material contains a metal and is adjacent to an area containing a substance having electromagnetic wave absorbing ability or a substance having electromagnetic wave absorbing ability.

  11. 7. The method of manufacturing an electronic device as described in 6 above, wherein the semiconductor precursor material is a metal oxide semiconductor precursor and is converted into a metal oxide semiconductor.

  12 12. The method for producing an electronic device as described in 11 above, wherein the metal oxide semiconductor precursor contains at least one of In, Zn, and Sn.

  13. 13. The method of manufacturing an electronic device as described in 11 or 12 above, wherein the metal oxide semiconductor precursor contains Ga or Al.

  14 7. The method of manufacturing an electronic device according to 6, wherein the semiconductor precursor material is an organic semiconductor precursor and is converted into an organic semiconductor.

  15. After forming an electrode containing a substance having electromagnetic wave absorbing ability and at least two functional layer precursor areas among an insulating film precursor area, a semiconductor precursor area, and a protective film precursor area, an electromagnetic wave is irradiated to form a functional layer precursor. 15. The method for manufacturing an electronic device according to any one of 1 to 14, wherein the functional layer is formed by simultaneously heating the body layer area.

  16. After forming an electrode precursor area containing an electromagnetic wave absorbing substance or an electromagnetic wave absorbing substance, and at least one functional layer precursor area among an insulating film precursor area, a semiconductor precursor area, and a protective film precursor area The manufacturing of the electronic device according to any one of 1 to 14, wherein the electrode and the functional layer are simultaneously formed by irradiating electromagnetic waves and simultaneously heating the electrode precursor area and the functional layer precursor area. Method.

  17. The electron according to any one of 6 to 16, wherein the transistor element has a bottom gate structure, and the gate electrode is formed of an area including a substance having an electromagnetic wave absorbing ability or a substance having an electromagnetic wave absorbing ability. Device manufacturing method.

  18. The electron according to any one of 5 to 16, wherein the transistor element has a bottom contact structure, and the gate electrode includes an area containing a substance having an electromagnetic wave absorbing ability or a substance having an electromagnetic wave absorbing ability. Device manufacturing method.

  19. The electron according to any one of 5 to 16, wherein the transistor element has a top gate structure, and the gate electrode is composed of an area containing a substance having an electromagnetic wave absorbing ability or a substance having an electromagnetic wave absorbing ability. Device manufacturing method.

  20. 20. The method for manufacturing an electronic device according to any one of 1 to 19, wherein the electromagnetic wave is a microwave (frequency: 0.3 to 50 GHz).

  21. Any one of the electrode precursor material, the semiconductor precursor material, the insulator precursor material, and the protective film precursor material of the transistor element is formed by coating. The manufacturing method of the electronic device of description.

  22. The substrate temperature of an electronic device is 50-200 degreeC, and coating-film surface temperature is 200-600 degreeC, The manufacturing method of the electronic device of any one of said 1-21, characterized by the above-mentioned.

  23. The method for manufacturing an electronic device according to any one of 1 to 22, wherein the substrate is a resin substrate.

  24. The shortest distance between the area (heat source area) containing an electromagnetic wave absorbing substance or an electromagnetic wave absorbing substance and the base of the electronic device is on the functional layer precursor area side where the electromagnetic wave is absorbed and heat is generated. 24. The manufacturing of an electronic device according to any one of 1 to 23 above, which is 1/200 to 10 times the longest distance between the boundary surface and the entire boundary of the functional layer precursor area to be heat-converted. Method.

  25. 25. An electronic device manufactured by the method for manufacturing an electronic device according to any one of 1 to 24 above.

  According to the present invention, it is possible to manufacture by a coating process (printing or IJ), there is no abnormal discharge due to electromagnetic wave irradiation, and at the same time, the electrode formation and the semiconductor formation process can be performed in one step, and the production efficiency and production stability are high It was possible to provide an electronic device manufacturing method with improved carrier mobility and on / off ratio and an electronic device obtained by the manufacturing method.

  The present invention has an electrode on a substrate and has an electromagnetic wave absorbing ability adjacent to or close to an area containing at least a portion of the heat conversion material or the heat conversion material, and the area containing the heat conversion material or the heat conversion material. In an electronic device manufacturing method in which an area including a substance having a substance or a substance having electromagnetic wave absorption ability is arranged, irradiated with electromagnetic waves, and heat conversion material is converted into a functional material by heat generated by the substance having electromagnetic wave absorption ability An electronic device manufacturing method and an electronic device obtained by the manufacturing method are characterized in that all the angles formed by the sides of the electrodes are larger than 90 ° and smaller than 180 °, or are curved surfaces.

  In the field of ceramics, it is already known to use the electromagnetic wave according to the present invention for sintering. When a material containing magnetism is irradiated with an electromagnetic wave, heat can be generated in accordance with the size of the loss portion of the complex permeability of the substance, and the temperature can be increased uniformly and in a short time.

  On the other hand, it is also well known that when an electromagnetic wave is irradiated onto a metal, free electrons start to move at a high frequency, so that arc discharge occurs and heating cannot be performed. Also, metals with high conductivity and loosely bound free electrons are more likely to discharge themselves and reflect electromagnetic waves due to the movement of free electrons. There was a problem that it was difficult to use as an electrode material.

  Here, the electrode of the electronic device refers to a gate electrode, a source electrode, a drain electrode, a pixel electrode, a storage capacitor electrode, a capacitor capacitor electrode, and the like.

  Based on such a technical background, the present inventors diligently studied the above problems, and as a result, all the angles formed by the sides of the electrodes were larger than 90 ° and smaller than 180 °, or curved surfaces (hereinafter, By making it larger than 90 ° and smaller than 180 °, or the curved surface is also called an obtuse angle, generation of an arc (abnormal discharge) at the time of electromagnetic wave irradiation is prevented, and cracks and constituent materials in the irradiation region based on abnormal discharge are generated. It has been found that the deterioration due to carbonization or the like is prevented and the production stability is improved. More preferably, the angles formed by the sides of the electrodes are all greater than 110 ° and less than 150 °.

  FIG. 1 shows a planar shape of a conventional electrode. FIG. 2 shows the planar shape of the electrode according to the present invention.

  In order to make the angle formed by the sides of the electrode obtuse, an electrode material such as ITO, Al, Cr or the like is sputtered to form a thin film, and then etched to form this shape by a photolithographic method, or these There is a method of discharging and drawing a fluid electrode material containing a metal by an ink jet method so as to have this shape.

  From the same viewpoint, electrode materials include so-called conductive metal oxides such as doped Si, In oxide, Zn oxide, and Sn oxide that exhibit relatively high conductivity from room temperature to high temperature due to degenerate conduction. Things are preferred. Further, if there is a portion having high resistance such as a grain boundary in the inside of these conductive metal oxides, there is a risk of causing discharge in that portion, so that those made of a single crystal are preferable.

  The heat conversion material means a precursor that is converted into various functional materials (layers) in an electronic device by heat, and specifically includes, for example, a semiconductor material precursor, an insulating material precursor, and an electrode material precursor. These are functional material precursors that are converted into semiconductors, insulating materials, electrodes, and the like by heat. The heat conversion material includes not only a material that reacts by heat but also a material that exhibits a so-called annealing effect.

  The substance having electromagnetic wave absorbing ability is, for example, a metal oxide, and the substance having electromagnetic wave absorbing ability is preferably a conductor. It seems that the electromagnetic wave is absorbed by Me-O bonds in the metal oxide (the metal itself is not absorbed).

  In addition, the metal oxide preferably contains at least oxides of In, Sn, and Zn because of its high conductivity, and since it has higher electromagnetic wave absorption ability, it contains at least In, Sn, particularly Sn oxide. It is preferable to contain.

  In particular, for example, when using ITO fine particles as a conductor, Sn oxide has a particularly high ability to absorb electromagnetic waves compared to In oxide and Zn oxide, so that the electrode pattern portion containing Sn oxide first becomes high temperature. . After forming a pattern of such a substance having electromagnetic wave absorbing ability, for example, a functional layer precursor (for example, a semiconductor precursor) area (thin film) is formed thereon and irradiated with electromagnetic waves, thereby being made of ITO. Not only the electrode pattern portion but also the vicinity thereof becomes high temperature, and for example, formation from a heat conversion material layer to a functional material layer (for example, a semiconductor layer) can be simultaneously performed by ITO.

  In addition, if an electrode material precursor area is formed according to the electrode pattern, an area including a heat conversion material is formed, and electromagnetic radiation is applied, both the electrode and the functional material layer are formed simultaneously.

  The area containing the substance having electromagnetic wave absorbing ability or the substance having electromagnetic wave absorbing ability is preferably an electrode.

  Examples of an electronic device in which an electrode containing a substance having electromagnetic wave absorbing ability or an area containing a substance having electromagnetic wave absorbing ability is used can include a thin film transistor, an organic electroluminescence element, a solar cell, a light emitting diode (LED), etc. The thin film transistor element of the present invention is preferable.

  Electrodes that have an electromagnetic wave absorbing ability or an area containing an electromagnetic wave absorbing substance are used as electrodes, and multiple functional layer areas such as insulating films, semiconductors, and protective films are formed. A thin film transistor element is preferred because a plurality of functional layers can be formed simultaneously by simultaneously heating the functional layer precursor layer area using the precursor area as a heat source.

  For example, after forming an electrode containing an electromagnetic wave absorbing substance or an electromagnetic wave absorbing substance and at least two functional layer precursor areas of an insulating film precursor area, a semiconductor precursor area, and a protective film precursor area Then, the electromagnetic wave is irradiated and the functional layer precursor layer area is simultaneously heated to form a plurality of functional layers simultaneously.

  In addition, the electrode is formed of a substance having electromagnetic wave absorbing ability or an electrode precursor containing a substance having electromagnetic wave absorbing ability, and at least one of an insulating film precursor area, a semiconductor precursor area, a protective film precursor area, and the like. After forming one functional layer precursor area, the electrode precursor area itself and the functional layer precursor area can be heated to form both the electrode and the functional layer by irradiating electromagnetic waves.

  Therefore, the present invention forms an area on a substrate with a substance having an electromagnetic wave absorbing ability, forms an area containing a functional material precursor on the area, and then irradiates the electromagnetic wave on the area, thereby improving the electromagnetic wave absorbing ability. The area formed with the substance is heated, and the area containing the functional material precursor is heated in the vicinity of the area containing the substance having the ability to absorb electromagnetic waves by the generated heat. It is a manufacturing method of an electronic device that performs conversion to a thin film.

  As a heat conversion material to be converted into a functional material or a film thereof, for example, as the first aspect of the present invention, there is a case where the heat conversion material is a semiconductor precursor material. The second aspect includes a case where the heat conversion material is an insulating film precursor material, and the third aspect includes a case where the heat conversion material is a protective film precursor material. Furthermore, the heat conversion material may be an electrode precursor material.

  Hereinafter, description will be made sequentially.

  As one embodiment of the present invention, an electrode pattern (area) containing a substance having electromagnetic wave absorbing ability or a substance having electromagnetic wave absorbing ability is formed on a substrate, and a semiconductor precursor material area ( After forming a thin film, an electrode and a semiconductor layer can be formed simultaneously by irradiating the film with an electromagnetic wave.

  The first aspect will be described with reference to the drawings.

  In FIG. 3, for example, a gate electrode 4 made of an ITO thin film is sputtered on a glass substrate 6 to form a thin film, for example, and then etched by photolithography so that the angle formed by the sides of the electrode becomes an obtuse angle. (The obtuse angle shape is not shown in the figure.) A gate electrode pattern is formed by patterning, and a gate insulating film 5 made of silicon oxide is formed thereon by sputtering or plasma CVD. This is shown (FIG. 3 (1)). Here, the conductive ITO has the ability to absorb electromagnetic waves.

Next, a metal ion-containing thin film that is a semiconductor precursor material, for example, In (NO ₃ ) ₃ , Zn (NO ₃ ) ₂ , Ga (NO ₃ ) ₃ (composition ratio mass 1 :) on the gate insulating film 5. 1: 1) A solution in which each is dissolved in acetonitrile is discharged by an ink jet apparatus to form an area of the semiconductor precursor material. This is dehydrated and dried to form, for example, a semiconductor precursor material area (thin film) 1 ′ having an average film thickness of 100 nm (FIG. 3 (2)).

  Thus, when a thin film containing a metal oxide semiconductor precursor material is formed on the channel region (area) on a gate electrode having an obtuse angle formed by the sides of the electrode, and then irradiated with electromagnetic waves , By the electromagnetic wave (microwave) irradiation, the electrode pattern made of ITO having electromagnetic wave absorbing ability absorbs this, so Joule heat is generated inside the electrode pattern, and Joule heat heats the vicinity by heat transfer, The metal oxide semiconductor precursor material film 1 ′ undergoes thermal oxidation in the presence of oxygen and is converted into the metal oxide semiconductor layer 1 (FIG. 3 (3)).

  Oxygen is required to produce a metal oxide semiconductor from a metal oxide semiconductor precursor material, and thermal oxidation occurs by irradiating electromagnetic waves in the presence of air (oxygen), resulting in a metal oxide semiconductor. The precursor material thin film is converted into a semiconductor film.

  In the case of using a substrate having low heat resistance such as a resin substrate, the substrate temperature is 50 to 200 ° C. by controlling the output of electromagnetic waves, the irradiation time, and the number of irradiations, and the surface temperature of the thin film containing the precursor It is preferable to process so that it may become 200-600 degreeC.

  Next, if the source electrode 2 and the drain electrode 3 are formed by, for example, gold vapor deposition, the thin film transistor element 14 is obtained (FIG. 3 (4)).

  Further, as a semiconductor layer, for example, an organic semiconductor precursor material, for example, a bicycloporphyrin compound as described in JP-A-2003-304014 is used to produce a semiconductor precursor layer, thereby generating heat due to electromagnetic wave absorption of the ITO electrode. Since it can be similarly converted into an organic semiconductor layer by thermal decomposition, an organic thin film transistor can be formed efficiently.

  An ITO thin film is a substance having an electromagnetic wave absorbing ability. However, when an electrode made of a normal metal material is used, an electromagnetic wave absorbing substance such as ITO is formed on the electrode because it does not absorb an electromagnetic wave. Thus, the electrode can be used as a heat source. Moreover, it is also possible to form an electrode pattern using the electrode precursor material described later, and to convert the electrode pattern into an electrode material by a substance having an electromagnetic wave absorbing ability such as ITO formed thereon.

  Conversely, on the ITO thin film, which is a metal oxide conductor, electrode material precursors such as metal nanoparticles (dispersed in JP-A-3-34211, JP-A-11-80647, etc.) It is also possible to apply electrodes to the electrodes by firing with the heat generated by ITO.

  In the above example, a semiconductor layer is formed as a functional layer by heat generation by electromagnetic wave irradiation from an electrode pattern having electromagnetic wave absorbing ability. For example, as in the second aspect, an insulating layer precursor material ( It is possible to convert and form this into an insulating layer using (described later).

  An example of this is shown in FIG. In the figure, a gate electrode 4 having an obtuse angle formed by a side of an electrode made of ITO is formed on a glass substrate 6 (the obtuse angle shape is not shown), and an insulating film precursor area 5 'is formed according to an insulating film pattern. However, it shows. ITO is formed on a glass substrate by sputtering, for example. By using a mask and patterning with a photoresist, a gate electrode 4 pattern having an obtuse angle formed by the sides of the electrode is obtained.

  As the insulating film precursor material, for example, when a silicon oxide film is formed, a metal compound material such as tetraethoxysilane, disilazane, polysilazane, and the like can be used. For example, tetraethoxysilane (TEOS) is made of the above ITO. A thin insulating film precursor material area 5 'is formed on the gate electrode pattern (FIG. 4 (1)).

  Examples of the insulating film precursor material include a precursor that forms a metal oxide film having a high relative dielectric constant, such as silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, and vanadium oxide. Of these, silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable. Metal nitrides such as silicon nitride and aluminum nitride can also be suitably used.

  As a precursor for forming these, for example, a so-called sol-gel film is preferable, and a metal of the above-described metal oxide, for example, a metal alkoxide such as silicon, a metal halide, or the like, which is called a sol-gel method, is an arbitrary organic solvent. Or the method of apply | coating and drying the liquid hydrolyzed and polycondensed with the acid catalyst etc. in water is used. According to this method, a spray coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, a coating method such as a die coating method, a printing method, a patterning method such as an inkjet method, etc. The wet process can be used depending on the material.

  When an organic compound film is used as the insulating film precursor material, for example, a material that forms an insulating organic film by polycondensation with heat, for example, a precursor material that forms an insulating film by polycondensation such as curable polyimide In addition, a photo-curing resin of a photo radical polymerization system, a photo cation polymerization system, or a copolymer containing an acrylonitrile component, a polyvinyl phenol containing a cross-linking agent, a polyvinyl alcohol, a novolac resin, etc. are formed by coating, These can be converted into insulating films. For example, as a curable polyimide, Kyocera Chemical Co., Ltd. CT4112, 4200, 4150, etc. can be obtained.

  The thickness of these insulating films is generally 50 nm to 3 μm, preferably 100 nm to 1 μm.

  After the formation of the insulating film precursor material area 5 ′, electromagnetic waves, preferably microwaves are then irradiated. By microwave irradiation, this is absorbed by a gate electrode material (ITO) having electromagnetic wave absorbing ability. Microwave absorption concentrates on a substance with high electromagnetic wave absorption ability. As a result, in the electrode material precursor pattern, the substance first generates Joule heat and is heated from the inside of the thin film, and this Joule heat is transferred to the vicinity. Thus, the adjacent insulating film precursor material area 'is heated, and the insulating film precursor material area is converted into the gate insulating film 5 (FIG. 4B).

TEOS, which is a precursor of SiO ₂ film, which is a typical insulating film material, has almost no electromagnetic wave absorbing ability, but an SiO ₂ bond is formed around (in the vicinity of) the gate electrode portion having electromagnetic wave absorbing ability to form an oxide insulating film. Thus, an electrode and an oxide insulating film can be formed simultaneously (FIG. 4 (3)).

  Also, if the insulating film is made of an absorptive metal (for example, Ti) as an oxide insulating film, for example, TiN, TiN is formed in the air, and at the same time, the sintering of the film proceeds due to its heat generation. become.

  Oxygen is required for the production of these insulating films, and thermal oxidation occurs by performing microwave irradiation in the presence of air (oxygen), thereby forming a highly insulating film (dielectric film).

  Since the heat resistance is low when using a resin substrate, the substrate temperature is 50 to 200 ° C. and the surface temperature of the thin film containing the precursor is 200 to 600 ° C. by controlling the output of electromagnetic waves, the irradiation time, and the number of irradiations. It is preferable to process so that it becomes.

  After the formation of the insulating layer, a thin film transistor element can be obtained in the same manner by performing semiconductor layer formation and source and drain electrode formation by a known method in the same process as in FIG. 3 (FIGS. 4 (3) to (5)). .

  In addition, after the formation of the insulating film precursor material area 5 ′, a metal oxide semiconductor precursor area is further formed, and after drying, electromagnetic waves, preferably microwaves are irradiated to absorb electromagnetic waves by the ITO electrode. With the heat generation involved, the metal oxide semiconductor precursor area as well as the insulating film precursor material area can be simultaneously thermally oxidized and converted into an insulating layer and a semiconductor layer, respectively.

  In the present invention, the shortest distance between an electromagnetic wave absorbing substance or an area containing an electromagnetic wave absorbing substance (heat source area) and the substrate of the electronic device is a function of heating and converting an area that absorbs electromagnetic waves and generates heat. The longest distance determined between the boundary surface on the layer precursor area side and the entire boundary of the functional layer precursor area to be heat-converted (between the boundary with any of the plural functional layer precursor areas) It is preferably 1/200 to 10 times.

  This is illustrated in FIG. FIG. 5 shows a function of converting a gate electrode 4 (an obtuse angle shape is not shown) formed on the substrate 6 via an intermediate layer 8 into an electrode side into an obtuse angle, a gate insulating layer 5, and a semiconductor layer. The layer precursor layer thin film 1 'is formed.

  The gate electrode with an obtuse angle formed by the sides of the electrode is an area (heat source area) containing a substance having an electromagnetic wave absorbing ability or a substance having an electromagnetic wave absorbing ability, and the shortest distance between the heat source area and the substrate is here The film thickness l of the intermediate layer formed on the gate electrode and the substrate corresponds to the shortest distance among the film thicknesses of the layers under the gate electrode.

  The maximum distance determined between the boundary of the functional layer precursor area where heat conversion is performed in the area where heat is generated by absorbing electromagnetic waves and the entire boundary of the functional layer precursor area where heat conversion is performed is the interface around the heat generation area. Is the longest distance between the boundary surface on the functional layer precursor area side to be heat-converted and the interface of the functional layer precursor area. This is the longest distance when any position on the functional layer precursor area interface is connected from an arbitrary position on the functional layer precursor area side where heat conversion is performed at the heat generation area interface in FIG. It hits. It is determined by looking at the entire interface of the area where each layer precursor is formed.

  In addition, understanding of the concept of the longest distance (D) determined between the boundary surface on the functional layer precursor area side where heat conversion is performed in the area that generates heat by absorbing electromagnetic waves and the functional layer precursor area boundary on which heat conversion is performed Therefore, another example is shown in FIG.

  In FIG. 5 (2), when an area that absorbs electromagnetic waves and generates heat is a source electrode 2 having an obtuse angle formed by the sides of the electrode or a drain electrode 3 having an obtuse angle formed by the sides of the electrode, the electromagnetic wave Between the boundary layer on the functional layer precursor area side where heat conversion is performed in the area that absorbs heat and generates heat and the entire boundary of the functional layer (semiconductor layer) precursor area formed in the channel region between the source electrode 2 and the drain electrode 3 The longest distance determined by is represented by D.

  D represents the longest distance from a material that absorbs electromagnetic waves and generates heat to a conversion material area that is converted into a functional layer by this heat generation. An electrode material composed of a substance that absorbs electromagnetic waves is an electrode material. Since the film thickness is in the range of 30 to 500 nm, when the conversion material area is far from the heat generating material, the heat conversion of the conversion material is not sufficient.

  That is, assuming that an area (heat source area) containing a substance having electromagnetic wave absorbing ability is, for example, a gate electrode, the heat conversion material is sufficiently converted into a functional material by propagation of heat generated by absorption of electromagnetic waves by the gate electrode, and In order to prevent damage to the substrate (particularly plastic substrate), the gate electrode to the substrate with respect to D indicating the distance from the heat source to the heat-converted, for example, insulator precursor layer or semiconductor precursor layer area It is preferable that the shortest distance 1 (to many, the thickness of the undercoat layer or the like formed on the resin support on which the gate electrode is formed) is 1/200 to 10 times.

  For example, even if there is a heat conversion material layer between the area (heat source area) containing a substance having electromagnetic wave absorbing ability and the substrate (support), or even on the opposite side of the substrate, it has electromagnetic wave absorbing ability The distance between the area containing the substance (heat source area) and the substrate, and the distance between the area containing the substance with electromagnetic wave absorption ability (heat source area) and the heat conversion material layer is converted into the functional layer by the heat conversion material layer. It shall be measured after forming.

  When in this range, the heat conversion material is sufficiently converted into a functional material in the vicinity of the area including the substance having the ability to absorb electromagnetic waves as a heat source, and the influence of heat on the substrate is small. When the ratio is less than 1/200, there is a concern about damage to the substrate, and on the other hand, the conversion of the heat conversion material into the functional material becomes insufficient. On the other hand, when the ratio exceeds 10 times, the performance of the element is still insufficient, and on the other hand, problems such as cracks begin to become apparent, and advantages such as flexibility as a thin film material may be lost.

  Therefore, in the case where the above relationship is satisfied, in the case where a protective film is formed over a transistor element, the present invention can also be applied to the formation of a protective film. For example, as a third aspect, a protective film can be formed by electromagnetic wave irradiation using a protective film precursor material as a heat conversion material. In forming these protective films, the same material as the insulating film precursor material described above is used.

  In the present invention, any substance having an electromagnetic wave absorbing ability can be used as a material that converts itself into an electrode material as a heat source that absorbs electromagnetic waves and generates Joule heat even if it is an electrode material precursor.

  In other words, the electrode itself and the adjacent functional layer can be converted into, for example, an insulating layer or a semiconductor layer by heat generated by electromagnetic waves from the formed electrode precursor area.

  As in FIG. 3, the electrode precursor area may be formed by a material having an electromagnetic wave absorption ability, for example, ITO fine particles, according to the gate electrode 4 pattern having an obtuse angle formed by the sides of the electrode. it can. For example, a dispersion of ITO particles in an organic solvent such as water or alcohol is formed on a substrate like a gate electrode pattern having an obtuse corner formed by coating (inkjet method) and dried to form an electrode precursor. Form the body area. Here, coating means not only so-called coating but also a wet process in which coating liquid, ink, and the like in a broad sense such as an ink jet method and a printing method are applied.

  A dispersion in which ITO particles are dispersed in an organic solvent such as water or alcohol can be drawn on a substrate by a coating (inkjet) method or the like using this as a paint.

For example, a metal ion-containing thin film, for example, In (NO ₃ ) ₃ , Zn (NO ₃ ), as the metal oxide semiconductor material precursor, on the electrode material precursor area formed according to the electrode pattern using ITO fine particles. ) ₂ , Ga (NO ₃ ) ₃ (1: 1: 1 by composition ratio) in water are each ejected by an ink jet device to form a film in the same manner, dried, and then irradiated with electromagnetic waves. Since Joule heat is generated inside the electrode pattern of the thin film, the electrode material precursor area is heated from the inside, the electrode material precursor is fired to the electrode, and the metal oxide semiconductor precursor is transferred by Joule heat transfer. The area also undergoes thermal oxidation in the presence of oxygen and is simultaneously converted into a metal oxide semiconductor layer.

  Electrode materials or precursor materials having electromagnetic wave absorbing ability are heated uniformly from the inside because electrons vibrate and generate Joule heat when irradiated with electromagnetic waves such as microwaves. On the other hand, substrates such as glass and resin hardly absorb heat in the microwave region, and therefore the substrate itself hardly generates heat. Therefore, when a plastic substrate is used, an electronic device such as a thin film transistor element can be manufactured without causing thermal deformation or deterioration of the substrate or the like by providing a heat generating layer while maintaining a predetermined distance or more as described above.

  As is common in electromagnetic heating such as microwaves, electromagnetic wave (microwave) absorption concentrates on strongly absorbing substances and can be heated to 500 to 600 ° C. in a very short time. Therefore, the substrate itself on which the electronic device is formed is hardly affected by heating due to electromagnetic waves, and can only raise the temperature of a substance having electromagnetic wave absorption ability in a short time. For example, when this is used as an electrode in a transistor element, It is possible to quickly convert itself and also, for example, adjacent thin-film metal oxide semiconductor precursor material areas into a semiconductor. Further, the heating temperature and the heating time can be controlled by the output of the microwave to be irradiated and the irradiation time, and can be adjusted according to the precursor material and the substrate material.

  When a metal oxide having electromagnetic wave absorbing ability is used as an electrode material precursor, a layer made of metal fine particles is further combined as an electrode material (metal does not absorb electromagnetic waves), for example, an electrode material made of ITO fine particles and metal fine particles An electrode precursor layer is formed by forming a precursor area according to an electrode pattern, or a material layer having these electromagnetic wave absorbing capabilities is formed on an electrode material precursor layer formed of, for example, metal fine particles to form an electrode precursor layer. Alternatively, a method of irradiating an electromagnetic wave to this and forming an electrode material may be employed.

  As described above, the aspect in which the heat conversion material in the functional layer is converted into the functional material by applying a substance having an electromagnetic wave absorbing ability to the gate electrode has been described. For example, in a thin film transistor, these electromagnetic waves are applied to the source electrode, the drain electrode, and the like. A thin film transistor element can also be formed by converting a heat conversion material into a functional material by applying a substance having an absorptivity. These aspects will be specifically described in Examples.

(Microwave irradiation)
In the present invention, microwaves are preferable as electromagnetic waves, and microwave irradiation is preferable. That is, after forming a thin film containing a metal that is an obtuse angled source / drain electrode pattern or a metal oxide semiconductor precursor formed by the sides of an electrode having electromagnetic wave absorbing ability, By irradiating microwaves (frequency 0.3 to 50 GHz), the electrode pattern thin film having electromagnetic wave absorption ability itself generates heat from the inside, thereby heating the electrode pattern and the adjacent metal oxide semiconductor precursor. A metal oxide semiconductor is produced from the pattern.

  In addition, when heating the thin film containing the metal oxide semiconductor precursor together with the pattern of the electrode precursor having electromagnetic wave absorbing ability of the present invention, it is possible to irradiate microwaves in the presence of oxygen in a short time. It is preferable when the oxidation reaction of the semiconductor precursor proceeds.

  In addition, in microwave irradiation, heat may be transferred to the base material due to heat conduction. Especially in the case of a base material with low heat resistance such as a resin substrate, the microwave output, irradiation time, and irradiation By controlling the number of times, the substrate temperature is preferably 50 to 200 ° C. and the surface temperature of the thin film containing the precursor is preferably 200 to 600 ° C. The surface temperature of the thin film, the temperature of the substrate, etc. can be measured with a surface thermometer using a thermocouple.

  In addition, the thin film containing the metal oxide semiconductor precursor is cleaned by a dry cleaning process such as oxygen plasma or UV ozone cleaning after the formation and before the microwave irradiation. It is also preferable that organic substances other than the metal component are excluded by decomposing and washing the causative organic substances.

  Generally, a microwave refers to an electromagnetic wave having a frequency of 0.3 to 50 GHz, and is used in 0.8 MHz and 1.5 GHz band, 2 GHz band, amateur radio, aircraft radar, etc. used in mobile communication. .2 GHz band, 2.4 GHz band used in microwave ovens, local radio, VICS, 3 GHz band used for ship radar, etc., and 5.6 GHz used for ETC communication are all electromagnetic waves that fall within the category of microwaves. is there.

  In the field of ceramics, it is already known to use such electromagnetic waves for sintering. When a material containing magnetism is irradiated with an electromagnetic wave, heat can be generated in accordance with the size of the loss portion of the complex permeability of the substance, and the temperature can be increased uniformly and in a short time. On the other hand, it is well known that when a metal is irradiated with microwaves, free electrons start to move at a high frequency, so that arc discharge occurs and heating cannot be performed.

  Based on such a background, the inventors, in addition to the electrode material precursor having electromagnetic wave absorbing ability of the present invention, a metal oxide semiconductor precursor, simultaneously, in a short time and uniformly, It has been found that it can be simultaneously converted into an electrode material and a metal oxide semiconductor by heating to high temperatures. Unlike the field of ceramics, metal oxide semiconductor precursors such as metal ion-containing solutions have almost no magnetism, and therefore there is no loss component related to electron and / or dipole motion such as Joule loss and / or dielectric loss. Although it is considered to be the main cause of the heat generation, the reason why such a phenomenon occurs in a thin film obtained by simply applying / drying a metal ion-containing solution is not clear.

  The thin film including the thin film electrode pattern and the metal oxide precursor is not necessarily formed by coating. However, in the present invention, forming these by coating includes forming an electrode by coating, and forming a semiconductor by coating. The production efficiency can be improved in the manufacture of the thin film transistor because it can be reduced to about 1, which is preferable.

(Substance with electromagnetic wave absorption ability)
In the present invention, as a substance having electromagnetic wave absorbing ability, one is a metal oxide material fine particle, preferably indium oxide, tin oxide, zinc oxide, IZO, ITO, etc., and at least an oxide of In or Sn. It is preferable to include. In the present invention, these substances capable of absorbing electromagnetic waves can be used as electrodes.

In the ITO film obtained by doping tin with indium oxide, the In: Sn atomic number ratio of the obtained ITO film is preferably adjusted to be in the range of 100: 0.5 to 100: 10. The atomic ratio of In: Sn can be determined by XPS measurement. In addition, a transparent conductive film (referred to as FTO film) obtained by doping tin oxide with fluorine (Sn: F atomic ratio in the range of 100: 0.01 to 100: 50), In ₂ O ₃ —ZnO-based amorphous A conductive film (In: Zn atomic ratio in the range of 100: 50 to 100: 5) or the like can be used. The atomic ratio can be determined by XPS measurement.

Conductive thin film made of metal oxide material fine particles with electromagnetic wave absorption ability can be formed by using vacuum deposition, sputtering, etc., metal alkoxides such as indium and tin, and organometallic compounds such as alkyl metals. It is also preferable to form by plasma CVD. It can also be produced by a coating method such as a sol-gel method using a metal alkoxide such as indium or tin, and an ITO film having excellent electrical conductivity in the order of 10 ⁻⁴ Ω · cm can be obtained. An electrode pattern is obtained in combination with an appropriate patterning method.

  The substance having electromagnetic wave absorbing ability may be a conductive thin film such as IZO or ITO formed by vapor deposition, sputtering or plasma CVD as described above. It may be an electrode precursor material that is a dispersion of metal oxide fine particles to be contained. In this case, since it becomes conductive by baking after film formation, according to the electrode pattern, for example, by a coating method such as an ink jet method. Then, after forming the electrode precursor area, this is fired to obtain an electrode material. Firing is preferably performed by microwave irradiation.

  As a dispersion of metal oxide fine particles containing at least an oxide of In and Sn, ITO fine particles are particularly preferable because they are very fine and highly dispersed. Since the Sn oxide has a high electromagnetic wave absorption capability and the electrode pattern portion containing the Sn oxide first has a high temperature, when it is included in the electrode material precursor, the vicinity of the electrode pattern portion also becomes high, which is preferable.

  These metal oxide fine particles are obtained, for example, from a gel-like material obtained by heating a solution whose pH has been adjusted, by a method such as heating and low-temperature sintering. The coating material (ink) dispersed in an appropriate solvent is a finely dispersed fine particle that does not cause clogging due to agglomeration or the like even when used for coating, ink jetting, printing, or the like.

  Such particles preferably have a particle size in the range of 5 to 50 nm.

These are commercially available and can also be obtained directly from the market. Examples thereof include NanoTek Slurry ITO, SnO _{2 and the} like manufactured by CI Kasei Co., Ltd.

  When these fine particle dispersions are used as an electrode material precursor, an electrode material such as ITO can be easily patterned by a coating method such as an ink jet method, and the surface temperature of the thin film is 200 to 600 ° C., regardless of the sputtering method or the like. Due to the relatively low temperature heat treatment or sintering, fine particles are crystallized to obtain a highly conductive thin film.

  In addition, examples of the electrode material precursor include at least an In, Sn, and Zn atom-containing compound, and examples thereof include metal salts, metal halide compounds, and organometallic compounds containing these metal atoms.

  As metal salts containing at least In, Sn, and Zn, nitrates, acetates, and the like can be suitably used, and as halogen metal compounds, chlorides, iodides, bromides, and the like can be suitably used.

  Among the electrode material precursors described above, preferred are indium, tin, zinc nitrates, halides, and alkoxides. Specific examples include indium nitrate, tin nitrate, zinc nitrate, indium chloride, tin chloride (divalent), tin chloride (tetravalent), zinc chloride, tri-i-propoxyindium, diethoxyzinc, bis (dipivaloylme Tanato) zinc, tetraethoxytin, tetra-i-propoxytin and the like.

  These electrode material precursors, for example, indium nitrate, tin nitrate, and the like, form an electrode material precursor area on the substrate according to the electrode pattern, and, similarly to the above, an insulating film precursor area serving as an insulating layer In the same manner as described above, the oxide formed in part in these electrode material precursors acts as a heating element. In addition, heat can be applied to the adjacent insulating film precursor area, which can be converted into an insulating film.

(Semiconductor precursor material)
In the present invention, a metal oxide semiconductor precursor or an organic semiconductor precursor material can also be used as the semiconductor precursor that is a heat conversion material.

  Examples of the metal oxide semiconductor precursor include a metal atom-containing compound, and examples of the metal atom-containing compound include metal salts, metal halide compounds, and organic metal compounds containing a metal atom.

  Metals of metal salts, halogen metal compounds, and organometallic compounds include Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl, Pb, Bi, Ce, Pr Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the like.

  Among these metal salts, it is preferable to contain any metal ion of indium, tin, and zinc, and they may be used in combination.

  Moreover, it is preferable that a gallium or aluminum is included as another metal.

  As metal salts, nitrates, acetates and the like can be suitably used, and as halogen metal compounds, chlorides, iodides, bromides and the like can be suitably used.

  Examples of the organometallic compound include those represented by the following general formula (I).

Formula (I) R ¹ _x MR ² _y R ³ _z
In the formula, M is a metal, R ¹ is an alkyl group, R ² is an alkoxy group, R ³ is a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group, and a ketooxy group (ketooxy complex group). X + y + z = m, x = 0 to m, or x = 0 to m−1, and y = 0 to m, z = 0. ~ M, each of which is 0 or a positive integer. Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group for R ² include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a 3,3,3-trifluoropropoxy group. Further, a hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the group selected from the β-diketone complex group, the β-ketocarboxylic acid ester complex group, the β-ketocarboxylic acid complex group, and the ketooxy group (ketooxy complex group) of R ³ include, for example, 2,4 -Pentanedione (also called acetylacetone or acetoacetone), 1,1,1,5,5,5-hexamethyl-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione , 1,1,1-trifluoro-2,4-pentanedione, and the β-ketocarboxylic acid ester complex group includes, for example, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetoacetic acid propyl ester, trimethylacetate Examples thereof include ethyl acetate, methyl trifluoroacetoacetate and the like, and examples of β-ketocarboxylic acid include For example, acetoacetic acid, trimethylacetoacetic acid and the like can be mentioned, and examples of ketooxy include acetooxy group (or acetoxy group), propionyloxy group, butyryloxy group, acryloyloxy group, methacryloyloxy group and the like. These groups preferably have 18 or less carbon atoms. Further, it may be linear or branched, or a hydrogen atom may be a fluorine atom. Among organometallic compounds, those having at least one oxygen in the molecule are preferable. As such, an organometallic compound containing at least one alkoxy group of R ² , a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group and a ketooxy group (ketooxy group) of R ³ Most preferred are metal compounds having at least one group selected from (complex groups). Among metal salts, nitrate is preferable. Nitrate is easily available as a high-purity product and has high solubility in water, which is preferable as a medium for use. Examples of nitrates include indium nitrate, tin nitrate, zinc nitrate, and gallium nitrate.

  Of the above metal oxide semiconductor precursors, metal nitrates, metal halides, and alkoxides are preferable. Specific examples include indium nitrate, zinc nitrate, gallium nitrate, tin nitrate, aluminum nitrate, indium chloride, zinc chloride, tin chloride (divalent), tin chloride (tetravalent), gallium chloride, aluminum chloride, tri-i-. Examples include propoxyindium, diethoxyzinc, bis (dipivaloylmethanato) zinc, tetraethoxytin, tetra-i-propoxytin, tri-i-propoxygallium, and tri-i-propoxyaluminum.

(Metal oxide semiconductor precursor thin film deposition method, patterning method)
In order to form a thin film containing a metal as a precursor of these metal oxide semiconductors, a known film formation method, vacuum deposition method, molecular beam epitaxial growth method, ion cluster beam method, low energy ion beam method, ion A plating method, a CVD method, a sputtering method, an atmospheric pressure plasma method, and the like can be used. However, in the present invention, a solution in which a metal salt, a halide, an organometallic compound, or the like is dissolved in an appropriate solvent is used on the substrate. It is preferable that the coating is continuously performed because productivity can be greatly improved. Also from this point, it is more preferable from the viewpoint of solubility to use a chloride, nitrate, acetate, metal alkoxide or the like as the metal compound.

  The solvent is not particularly limited as long as it dissolves the metal compound to be used in addition to water, but water, alcohols such as ethanol, propanol and ethylene glycol, ethers such as tetrahydrofuran and dioxane, acetic acid, etc. Esters such as methyl and ethyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, glycol ethers such as diethylene glycol monomethyl ether, acetonitrile, and aromatic hydrocarbon solvents such as xylene and toluene, o-dichlorobenzene , Aromatic solvents such as nitrobenzene and m-cresol, aliphatic hydrocarbon solvents such as hexane, cyclohexane and tridecane, α-terpineol, and alkyl halide solvents such as chloroform and 1,2-dichloroethane, N Methylpyrrolidone, can be preferably used carbon disulfide and the like.

  When a metal halide and / or metal alkoxide is used, a solvent having a relatively high polarity is preferable. Among them, water having a boiling point of 100 ° C. or less, alcohols such as ethanol and propanol, acetonitrile, or a mixture thereof is used for drying. Since the temperature can be lowered, it can be applied to the resin substrate, which is more preferable.

  Addition of metal alkoxide and various ligands such as alkanolamines, α-hydroxy ketones, β-diketones and other chelating ligands in the solvent stabilizes the metal alkoxide and the solubility of the carboxylate. It is preferable to add in a range that does not cause adverse effects.

  As a method of forming a thin film by applying a liquid containing a semiconductor precursor material on a substrate, a spin coating method, a spray coating method, a blade coating method, a dip coating method, a casting method, a bar coating method, a die coating method, etc. Examples of the coating method include a method of coating in a broad sense such as a printing method such as a relief printing plate, an intaglio plate, a planographic printing method, a screen printing method, and an ink jet printing method, and a method of patterning by this. Alternatively, the coating film may be patterned by photolithography, laser ablation, or the like. Among these, the ink jet method, spray coating method, etc. which can apply | coat a thin film are preferable.

  In the case of film formation, a thin film of a metal oxide precursor is formed by volatilizing the solvent at about 150 ° C. after coating. In addition, when dropping the solution, it is preferable that the substrate itself is heated to about 150 ° C. because two processes of coating and drying can be performed simultaneously.

(Composition ratio of metal)
As a preferred metal composition ratio, when In is 1, Zn _y Sn _1-y (where y is a positive number from 0 to ₁ ) is 0.2 to 5, preferably 0.5 to 2. . Furthermore, when In is set to 1, the composition ratio of Ga is 0.2 to 5, preferably 0.5 to 2.

  Moreover, the film thickness of the thin film containing the metal used as a precursor is 1-200 nm, More preferably, it is 5-100 nm.

(Amorphous oxide)
As the metal oxide semiconductor to be formed, any state of single crystal, polycrystal, and amorphous can be used, but an amorphous thin film is preferably used.

The electron carrier concentration of an amorphous oxide, which is a metal oxide according to the present invention, formed from a metal compound material that is a precursor of a metal oxide semiconductor only needs to be less than 10 ¹⁸ / cm ³ . The electron carrier concentration is a value when measured at room temperature. The room temperature is, for example, 25 ° C., specifically, a certain temperature appropriately selected from the range of about 0 ° C. to 40 ° C. Note that the electron carrier concentration of the amorphous oxide according to the present invention does not need to satisfy less than 10 ¹⁸ / cm ³ in the entire range of 0 ° C. to 40 ° C. For example, a carrier electron density of less than 10 ¹⁸ / cm ³ may be realized at 25 ° C. Further, when the electron carrier concentration is further reduced to 10 ¹⁷ / cm ³ or less, more preferably 10 ¹⁶ / cm ³ or less, a normally-off TFT can be obtained with a high yield.

  The electron carrier concentration can be measured by Hall effect measurement.

  The film thickness of the semiconductor that is a metal oxide is not particularly limited, but the characteristics of the obtained transistor are often greatly influenced by the film thickness of the semiconductor film, and the film thickness varies depending on the semiconductor. Generally, 1 μm or less, particularly 10 to 300 nm is preferable.

In the present invention, the precursor material, composition ratio, production conditions, and the like are controlled so that, for example, the electron carrier concentration is 10 ¹² / cm ³ or more and less than 10 ¹⁸ / cm ³ . More preferably, it is in the range of 10 ¹³ / cm ³ or more and 10 ¹⁷ / cm ³ or less, and more preferably 10 ¹⁵ / cm ³ or more and 10 ¹⁶ / cm ³ or less.

(Other semiconductor layers)
In the present invention, when an insulating layer is formed using an electrode or an insulating layer precursor material as a heat conversion material, the semiconductor layer may be formed by a known method.

  For example, it is not necessary to use the method of the present invention in which a semiconductor layer is formed by using a substance having an electromagnetic wave absorbing ability as an electrode by using microwave irradiation as a heat source, and a semiconductor precursor using the metal oxide semiconductor precursor material described above. After the area is formed, it can be formed by a method of thermally oxidizing, for example, thermal oxidation, plasma oxidation, or irradiation with ultraviolet rays in the presence of oxygen.

  For example, when using plasma oxidation, the atmospheric pressure plasma method is preferable, and in the plasma oxidation, a substrate on which a thin film containing a precursor is formed is heated in a range of 150 to 300 ° C., and an atmospheric pressure, argon gas, An inert gas such as nitrogen gas is used as a discharge gas, together with this, a reaction gas (a gas containing oxygen) is introduced into the discharge space, a high-frequency electric field is applied to excite the discharge gas, generate plasma, Oxygen plasma is generated by contact, and this is exposed to the surface of the substrate to perform plasma oxidation of the semiconductor precursor material. Under atmospheric pressure represents a pressure of 20 to 110 kPa, preferably 93 to 104 kPa.

  When an oxygen plasma is generated using a gas containing oxygen as a reactive gas by the atmospheric pressure plasma method, the gas used varies depending on the type of thin film, but basically a discharge gas (inert gas) and an oxidizing gas. It is a mixed gas. When performing plasma oxidation, it is preferable to contain 0.01-10 volume% of oxygen gas with respect to mixed gas as oxidizing gas. Although it is more preferable that it is 0.1-10 volume%, More preferably, it is 0.1-5 volume%.

  Examples of the inert gas include Group 18 elements of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, nitrogen gas, and the like, but helium, argon, and nitrogen gas are preferably used. It is done.

  The plasma method under atmospheric pressure is described in JP-A-11-61406, JP-A-11-133205, JP-A-2000-121804, JP-A-2000-147209, JP-A-2000-185362, WO2006 / 129461, etc. Are listed.

(Other organic semiconductor layers)
In the second aspect, an organic semiconductor thin film (layer) can be used as the semiconductor layer.

  As the organic semiconductor material, various condensed polycyclic aromatic compounds and conjugated compounds described later can be applied.

  Examples of the condensed polycyclic aromatic compound as the organic semiconductor material include, for example, anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, obalene, circumcomanthracene, Examples thereof include compounds such as bisanthene, zestrene, heptazeslen, pyranthrene, violanthene, isoviolanthene, cacobiphenyl, phthalocyanine, and porphyrin, and derivatives thereof.

  Examples of the conjugated compound include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, tetrathiafulvalene compound, quinone Compounds, cyano compounds such as tetracyanoquinodimethane, fullerenes and derivatives or mixtures thereof. In addition, a bicyclo compound (bicycloporphyrin compound) having a cyclic structure as described in JP-A-2003-304014 can also be used.

  As a method of forming these organic semiconductor layers, it can be formed by a known method, for example, vacuum deposition, MBE (Molecular Beam Epitaxy), ion cluster beam method, low energy ion beam method, ion plating method, Sputtering method, CVD (Chemical Vapor Deposition), laser deposition, electron beam deposition, electrodeposition, casting method from solution, spin coating, dip coating, bar coating method, die coating method, spray coating method, LB method, etc. Examples thereof include screen printing, ink jet printing, blade coating and the like.

  Among these, the spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method and the like that can form a thin film easily and precisely using an organic semiconductor solution are preferred in terms of productivity. . In particular, when the organic semiconductor layer is formed by the pattern forming method according to the present invention, it is preferable to apply and apply the organic semiconductor solution to the patterned substrate surface.

  The organic solvent used in preparing the organic semiconductor solution is preferably an aromatic hydrocarbon, an aromatic halogenated hydrocarbon, an aliphatic hydrocarbon or an aliphatic halogenated hydrocarbon, an aromatic hydrocarbon, an aromatic halogenated More preferred are hydrocarbons or aliphatic hydrocarbons.

  Examples of the aromatic hydrocarbon organic solvent include toluene, xylene, mesitylene, and methylnaphthalene, but the present invention is not limited thereto.

  Aliphatic hydrocarbons include octane, 4-methylheptane, 2-methylheptane, 3-methylheptane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethyl. Although hexanecyclohexane, cyclopentane, methylcyclohexane, etc. can be mentioned, this invention is not limited to these.

  Examples of the organic solvent for the aliphatic halogenated hydrocarbon include chloroform, bromoform, dichloromethane, dichloroethane, trichloroethane, difluoroethane, fluorochloroethane, chloropropane, dichloropropane, chloropentane, and chlorohexane. It is not limited to these.

  These organic solvents used in the present invention may be used alone or in combination of two or more. The organic solvent preferably has a boiling point of 50 ° C to 250 ° C.

  In addition, as described in Advanced Material 1999 No. 6, p. 480 to 483, a precursor such as pentacene is soluble in a solvent, a target organic material formed by heat treatment of a precursor film formed by coating The thin film may be formed.

  The film thickness of these organic semiconductor layers is not particularly limited, but the characteristics of the obtained transistor are often greatly influenced by the film thickness of the organic semiconductor layer, and the film thickness varies depending on the organic semiconductor. Generally, 1 μm or less, particularly 10 to 300 nm is preferable.

  Furthermore, according to the organic semiconductor device of the present invention, at least one of the gate electrode and the source / drain electrode is formed by the method of manufacturing an organic semiconductor device of the present invention, so that a low-resistance electrode requires a high temperature. Instead, it can be formed without causing deterioration of the characteristics of the organic semiconductor layer material layer.

  In the case of forming an organic semiconductor layer, prior to the formation of the organic semiconductor layer, a surface treatment made of an organic material is applied to the region where the organic semiconductor layer is formed on the surface of the substrate made of, for example, a metal oxide, such as an undercoat. Is preferred. As the surface treatment made of an organic substance, one that is physically adsorbed on the substrate surface, a surfactant, or the like can be used. It is particularly preferable to form a monomolecular film by physical adsorption or chemical adsorption on the surface of the substrate on which an organic semiconductor layer is formed, for example, an insulating film or the like. Of these, surface treatment with a silane coupling agent is preferred. A silane coupling agent forms a monomolecular film by bonding with an oxide surface serving as an insulating layer by a chemical reaction.

In particular, silane coupling agents such as octyltrichlorosilane, octadecyltrichlorosilane, phenyltrichlorosilane, octyltriethoxysilane, silazanes such as hexamethyldisilazane,
The following compounds are also preferable silane coupling agents.

  A surface treatment with a titanium coupling agent such as octyltrichlorotitanium, octyltriisopropoxytitanium, or the like is also preferable.

  Next, other elements constituting the thin film transistor will be described below.

(electrode)
In the present invention, the conductive material used for the electrodes such as the source electrode, the drain electrode, and the gate electrode constituting the TFT element is an electrode material having an electromagnetic wave absorbing ability produced by the above method, for example, a metal oxide conductive material. In addition to materials, other electrode materials can be used. For example, after the gate electrode and the gate insulating layer are formed by the microwave irradiation according to the method of the present invention according to the first embodiment, the source and drain electrodes may not necessarily be the same method.

  Even when an electrode material having electromagnetic wave absorbing ability is used for the source and drain electrodes and the semiconductor precursor material is a semiconductor layer, there is no limitation on the electrode material of the gate electrode, for example.

  Other electrode materials are only required to have conductivity at a level that can be used as an electrode, and are not particularly limited. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, Palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, indium tin oxide (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon paste , Lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium-potassium alloy, magnesium, lithium, aluminum, magnesium / copper mixture, magnesium Neshiumu / silver mixture, a magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide mixture, a lithium / aluminum mixture, or the like is used.

  Moreover, as a conductive material, a conductive polymer, metal fine particles, or the like can be suitably used. As the dispersion containing metal fine particles, for example, a known conductive paste or the like may be used, but preferably a dispersion containing metal fine particles having a particle diameter of 1 nm to 50 nm, preferably 1 nm to 10 nm. In order to form an electrode from metal fine particles, the above-described method can be used in the same manner, and the metal described above can be used as the material of the metal fine particles.

  Further, as described above, these electrode materials and the substance having the electromagnetic wave absorbing ability can be combined and used as an electrode material having an electromagnetic wave absorbing ability.

(Method for forming electrodes, etc.)
As a method for forming these electrodes, a conductive thin film formed using a method such as vapor deposition or sputtering using the above as a raw material has an obtuse angle formed by the sides of the electrodes using a known photolithography method or a lift-off method. And a method of forming a resist on a metal foil such as aluminum or copper by means of thermal transfer, ink jet or the like and etching to form an electrode having an obtuse angle formed by the sides of the electrode. Alternatively, a conductive polymer solution or dispersion, a dispersion containing metal fine particles, or the like may be subjected to electrode patterning by an inkjet method so that the angle formed by the sides of the electrode is obtuse, or from the coating film to a lithograph or laser An electrode having an obtuse angle formed by the sides of the electrode may be formed by ablation or the like. Further, a method of patterning an electrode with conductive ink containing a conductive polymer or metal fine particles, a conductive paste, etc., so that the corners of the electrodes form an obtuse angle by a printing method such as relief printing, intaglio printing, planographic printing, and screen printing is also used. Can do.

  As a method of forming an electrode such as a source, drain, or gate electrode, a gate, or a source bus line without patterning a metal thin film using a photosensitive resin such as etching or lift-off, there is a method by an electroless plating method. Are known.

  Regarding the method of forming an electrode by electroless plating, as described in Japanese Patent Application Laid-Open No. 2004-158805, the portion where the electrode is provided contains a plating catalyst that causes electroless plating by acting with a plating agent. After the liquid is subjected to electrode patterning by, for example, a printing method (including ink jet printing) such that the corners formed by the sides of the electrode are obtuse, a plating agent is brought into contact with a portion where the electrode is provided. If it does so, electroless plating will be performed to the said part by the contact of the said catalyst and a plating agent, and an electrode pattern will be formed.

  The application of the electroless plating catalyst and the plating agent may be reversed, and the pattern formation may be performed either. However, a method of forming a plating catalyst pattern and applying the plating agent to this is preferable.

  As the printing method, for example, screen printing, planographic printing, letterpress printing, intaglio printing, printing by ink jet printing, or the like is used.

(Gate insulation film)
When the oxide insulating film is not formed by the method of the present invention, various insulating films can be used as the gate insulating film of the thin film transistor. In particular, an inorganic oxide film having a high relative dielectric constant is preferable. Inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, Examples thereof include barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, and trioxide yttrium. Of these, silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

  Examples of the method for forming the film include a vacuum process, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, an atmospheric pressure plasma method, and the like, spraying Examples include a wet process such as a coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, a coating method such as a die coating method, and a patterning method such as printing or inkjet. Can be used depending on the material.

  The wet process is a method of applying and drying a liquid in which fine particles of inorganic oxide are dispersed in an arbitrary organic solvent or water using a dispersion aid such as a surfactant as required, or an oxide precursor, for example, A so-called sol-gel method in which a solution of an alkoxide body is applied and dried is used.

  Of these, the atmospheric pressure plasma method described above is preferable.

  It is also preferable that the gate insulating film (layer) is composed of an anodized film or the anodized film and an insulating film. The anodized film is preferably sealed. The anodized film is formed by anodizing a metal that can be anodized by a known method.

  Examples of the metal that can be anodized include aluminum and tantalum, and the anodizing method is not particularly limited, and a known method can be used.

  Examples of organic compound films include polyimides, polyamides, polyesters, polyacrylates, photo-radical polymerization-type, photo-cation polymerization-type photo-curing resins, copolymers containing acrylonitrile components, polyvinyl phenol, polyvinyl alcohol, novolac resins, etc. Can also be used.

  An inorganic oxide film and an organic oxide film can be laminated and used together. The thickness of these insulating films is generally 50 nm to 3 μm, preferably 100 nm to 1 μm.

[Protective layer]
It is also possible to provide a protective layer on the organic thin film transistor element. Examples of the protective layer include inorganic oxides or inorganic nitrides, metal thin films such as aluminum, polymer films with low gas permeability, and laminates thereof. Improves. As a method for forming these protective layers, the same method as the method for forming the gate insulating film described above can be used. Further, the protective layer may be provided by a method such as simply laminating a film in which various inorganic oxides are laminated on a polymer film.

(substrate)
Various materials can be used as the support material constituting the substrate, for example, ceramic substrates such as glass, quartz, aluminum oxide, sapphire, silicon nitride, silicon carbide, silicon, germanium, gallium arsenide, gallium phosphide. In addition, a semiconductor substrate such as gallium nitrogen, paper, non-woven fabric, and the like can be used. In the present invention, the support is preferably made of a resin, for example, a plastic film sheet can be used. Examples of plastic films include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose. Examples include films made of triacetate (TAC), cellulose acetate propionate (CAP), and the like. By using a plastic film, the weight can be reduced as compared with the case of using a glass substrate, the portability can be improved, and the resistance to impact can be improved.

  An element protective layer can be provided on the thin film transistor element of the present invention. Examples of the protective layer include the inorganic oxides and inorganic nitrides described above, and it is preferable to form the protective layer by the atmospheric pressure plasma method described above.

(Element structure)
FIG. 6 is a diagram showing a typical configuration of a thin film transistor element.

  FIG. 5A shows a source electrode 2 having an obtuse angle formed by the electrode sides on the support 6 (the obtuse angle shape is not shown), and a drain electrode 3 having an obtuse angle formed by the electrode sides. (The obtuse angle shape is not shown) is formed, using this as a base material (substrate), the semiconductor layer 1 is formed between both electrodes, the insulating layer 5 is formed thereon, and the electrode sides are further formed thereon The field effect thin film transistor is formed by forming the gate electrode 4 (the obtuse angle shape is not shown) having an obtuse angle formed by. FIG. 2B shows the semiconductor layer 1 formed between the electrodes in FIG. 1A so as to cover the entire surface of the electrode and the support using a coating method or the like. (C) First, the semiconductor layer 1 is formed on the support 6, and then the source electrode 2 having an obtuse angle formed by the sides of the electrode (the obtuse angle is not shown), and the angle formed by the sides of the electrode Represents an obtuse-angled drain electrode 3 (the obtuse angle shape is not shown), an insulating layer 5, and a gate electrode 4 having an obtuse angle formed by the sides of the electrode (the obtuse angle shape is not shown). .

  FIG. 6D shows a gate electrode 4 having an obtuse angle formed by the electrode sides on the support 6 (the obtuse angle shape is not shown) and an insulating layer 5 formed thereon, on which the electrode sides are formed. The source electrode 2 having an obtuse angle formed by the electrode (the obtuse angle shape is not shown) and the drain electrode 3 having an obtuse angle formed by the sides of the electrode are formed (the obtuse angle shape is not shown). A semiconductor layer 1 is formed therebetween. In addition, the configuration as shown in FIGS.

  Among the above, the present invention can be applied to the process of simultaneously forming the gate electrode and the insulating layer, the semiconductor layer, and the source and drain electrodes and the semiconductor layer in FIG. Although not shown here, it can also be used in the process of forming a protective layer or the like.

  In the present invention, the transistor element preferably has a bottom gate structure (FIGS. 6D to 6F). In the case of this structure, it is preferable to use a substance that absorbs electromagnetic waves for the gate electrode, since this can be used as a heat source and a plurality of layers such as a (gate) insulating layer and a semiconductor layer can be simultaneously converted from a heat conversion material to a functional layer.

  In addition, the bottom contact type in which the source / drain electrode is in front of the organic semiconductor layer as viewed from the gate electrode (FIGS. 6C and 6E, etc.) is preferable, and the electrode including the gate electrode, the source and drain electrodes, Since the formation of the insulating layer and the like can be separated from the formation of the semiconductor layer, it is preferable that the conversion to the electrode material and the insulating layer is different from the conversion condition to the semiconductor layer because the respective conversions can be performed sufficiently.

  In the case of the top gate structure (FIGS. 6A to 6C), the gate electrode has a structure far from the substrate, and when the substrate is a plastic substrate, from the viewpoint of thermal deformation or alteration of the substrate. preferable.

  FIG. 7 is a schematic equivalent circuit diagram of an example of a thin film transistor sheet 10 which is an electronic device in which a plurality of thin film transistor elements are arranged.

  The thin film transistor sheet 10 has a large number of thin film transistor elements 14 arranged in a matrix. Reference numeral 11 denotes a gate bus line of the gate electrode of each thin film transistor element 14, and reference numeral 12 denotes a source bus line of the source electrode of each thin film transistor element 14. An output element 16 is connected to the drain electrode of each thin film transistor element 14, and the output element 16 is, for example, a liquid crystal or an electrophoretic element, and constitutes a pixel in the display device. In the illustrated example, a liquid crystal is shown as an output element 16 by an equivalent circuit composed of a resistor and a capacitor. 15 is a storage capacitor, 17 is a vertical drive circuit, and 18 is a horizontal drive circuit.

  The method of the present invention can be used to produce such a thin film transistor sheet in which TFT elements are two-dimensionally arranged on a support.

  Moreover, the manufacturing method of the electronic device of this invention is applicable to any electronic device, for example, it can apply to an organic electroluminescent element (organic EL element) etc.

  The organic EL element has a configuration in which an organic layer that emits light is stacked and sandwiched between two electrodes on a substrate, and at least one of the electrodes is formed of a transparent electrode for light extraction.

  For example, the organic EL element is most simply composed of an anode / light-emitting layer / cathode, but usually the organic layer has functional separation such as a hole transport layer, a light-emitting layer, and an electron transport layer in order to increase the light emission efficiency. It has a laminated structure of various functional layers.

  The organic layer and each thin film have a film thickness ranging from 1 nm to several μm. In addition to the above, the electron blocking layer, the hole blocking layer, the buffer layer, and other necessary layers are arranged in a predetermined layer order. They are stacked so that carriers such as holes and electrons injected from both electrodes can move smoothly.

  In each of these organic layers constituting the organic EL device, the organic light emitting material contained in the light emitting layer includes aromatic heterocyclic compounds such as carbazole, carboline, diazacarbazole, triarylamine derivatives, stilbene derivatives, polyarylenes. , Aromatic condensed polycyclic compounds, aromatic heterocondensed ring compounds, metal complex compounds, etc., and single oligo compounds or composite oligo compounds thereof, but are not limited to this in the present invention and are widely known. Materials can be used.

  In the light emitting layer (film forming material), preferably about 0.1 to 20% by mass of a dopant may be included in the light emitting material. Examples of the dopant include known fluorescent dyes such as perylene derivatives and pyrene derivatives, and in the case of phosphorescent light emitting layers, for example, tris (2-phenylpyridine) iridium, bis (2-phenylpyridine) (acetylacetonate). A complex compound such as an orthometalated iridium complex represented by iridium, bis (2,4-difluorophenylpyridine) (picolinato) iridium, and the like is similarly contained in an amount of about 0.1 to 20% by mass. The thickness of the light emitting layer ranges from 1 nm to several hundred nm.

  Examples of the material used in the hole injection / transport layer include phthalocyanine derivatives, heterocyclic azoles, aromatic tertiary amines, polyvinyl carbazole, polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT: PSS), and the like. Polymer materials such as conductive polymers are also used for the light emitting layer, for example, carbazole-based light emitting materials such as 4,4′-dicarbazolylbiphenyl, 1,3-dicarbazolylbenzene, (di ) Low molecular light emitting materials represented by pyrene-based light emitting materials such as azacarbazoles, 1,3,5-tripyrenylbenzene, polymer light emitting materials represented by polyphenylene vinylenes, polyfluorenes, polyvinyl carbazoles, etc. Etc.

  Examples of the electron injection / transport layer material include metal complex compounds such as 8-hydroxyquinolinate lithium and bis (8-hydroxyquinolinate) zinc, and nitrogen-containing five-membered ring derivatives listed below. That is, oxazole, thiazole, oxadiazole, thiadiazole or triazole derivatives are preferred. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1 -Phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5-bis ( 1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1 , 3,4-thiadiazole, 1,4-bis [2- (5-phenyl) Asiazolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4 -Triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like.

  These organic materials preferably have a crosslinkable group such as a vinyl group. Since a material having a crosslinkable group is crosslinked by heat or light, it can be easily applied, and is crosslinked to form a network polymer. Therefore, the layer is preferably insolubilized when applied and laminated thereon.

  That is, a precursor layer is formed as a precursor of the organic material layer by coating, and this can be similarly made into each functional layer by proceeding with crosslinking by microwave heating with an electrode material having electromagnetic wave absorbing ability.

  The film thickness of the organic EL element and each organic layer is required to be about 0.05 to 0.3 μm, and preferably about 0.1 to 0.2 μm.

  The organic layer (organic EL functional layers) may be formed by any means such as vapor deposition and coating, but coating and printing are preferred. Coating is performed by spin coating, transfer coating, and extrusion coating. Etc. can be used. In consideration of material use efficiency, a method capable of applying a pattern such as transfer coating and extrusion coating is preferable, and transfer coating is particularly preferable.

  Moreover, screen printing, offset printing, inkjet printing, etc. can be used for printing. As the display element, a thin film, a small element size, and high-precision high-definition printing such as offset printing and inkjet printing are preferable in consideration of overlapping RGB patterns.

  Each organic material has its own solubility characteristics (solubility parameters, ionization potential, polarity), and there are limitations on the solvents that can be dissolved. In this case, since the solubility is different from each other, the concentration cannot be generally determined. However, depending on the organic EL material to be formed into a film, a solvent suitable for the above conditions can be used. For example, a halogenated hydrocarbon solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, dibutyl ether, tetrahydrofuran, dioxane, anisole, etc. Ether solvents, methanol, alcohol solvents such as ethanol, isopropanol, butanol, cyclohexanol, 2-methoxyethanol, ethylene glycol, and glycerin, and aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene Paraffin solvents such as hexane, octane, decane and tetralin, ester solvents such as ethyl acetate, butyl acetate and amyl acetate, amide systems such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone Examples thereof include solvents, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, amine solvents such as pyridine, quinoline and aniline, nitrile solvents such as acetonitrile and valeronitrile, and sulfur solvents such as thiophene and carbon disulfide.

  In addition, the solvent which can be used is not restricted to these, You may mix and use 2 or more types of these as a solvent.

  Among these, preferable examples of the organic EL material are different depending on each functional layer material. However, as a good solvent, for example, an aromatic solvent, a halogen solvent, an ether solvent, and the like are preferable. Aromatic solvents and ether solvents. In addition, examples of the poor solvent include alcohol solvents, ketone solvents, paraffin solvents, and the like. Among them, alcohol solvents and paraffin solvents are used.

  Of the two electrodes, those having a work function larger than 4 eV are suitable as the conductive material used for the anode for injecting holes, such as silver, gold, platinum, palladium, and their alloys, oxidation Metal oxides such as tin, indium oxide and ITO, and organic conductive resins such as polythiophene and polypyrrole are used. It is preferable that it is translucent, and ITO is preferable as a transparent electrode. As a method for forming the ITO transparent electrode, mask vapor deposition or photolithography patterning can be used, but is not limited thereto.

  Further, as the conductive material used as the cathode, those having a work function smaller than 4 eV are suitable, and examples thereof include magnesium and aluminum. Typical examples of the alloy include magnesium / silver and lithium / aluminum. The formation method can be mask vapor deposition, photolithography patterning, plating, printing, or the like, but is not limited thereto.

  According to the present invention, even in an electronic device such as an organic EL element having such a configuration, for example, by using an electromagnetic wave irradiation, each functional layer precursor layer using an electrode having an electromagnetic wave absorbing ability or an electrode precursor material is used. Can be converted into a functional layer.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1
Manufacturing Example of Bottom Gate / Top Contact Thin Film Transistor FIG. 3 is a schematic sectional view showing a manufacturing process.

  As a support 6, an ITO film was formed by sputtering using a glass substrate, and then etched by photolithography so that the angle formed by the sides of the electrode was an arc, and patterned to form a gate electrode 4 ( Thickness 100 nm).

  Next, a gate insulating film 5 made of silicon oxide having a thickness of 200 nm was formed by atmospheric pressure plasma CVD (FIG. 3A). As the atmospheric pressure plasma processing apparatus, an apparatus according to FIG. 6 described in JP-A No. 2003-303520 was used.

(Used gas)
Inert gas: helium 98.25% by volume
Reactive gas: oxygen gas 1.5 volume%
Reactive gas: Tetraethoxysilane vapor (bubbled with helium gas) 0.25% by volume
(Discharge conditions)
High frequency power supply: 13.56 MHz
Discharge output: 10 W / cm ²
(Electrode condition)
The electrode is coated with 1 mm of alumina by ceramic spraying on a stainless steel jacket roll base material having cooling means with cooling water, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried, and then sealed by ultraviolet irradiation. This is a roll electrode having a dielectric (relative permittivity of 10) that has been subjected to hole treatment and has a smooth surface and an Rmax of 5 μm, and is grounded. On the other hand, as the application electrode, a hollow rectangular stainless steel pipe was coated with the same dielectric as described above under the same conditions.

  Next, as a semiconductor precursor material, a solution obtained by dissolving 0.8 g of the following bicycloporphyrin compound in 1.25 g of chloroform is used as an ink, and is ejected to the channel forming portion on the gate insulating film by an ink jet method and dried to form a film. Then, a semiconductor precursor material area (thin film) 1 ′ was formed (thickness 30 nm, FIG. 3 (2)).

  Thereafter, the substrate was irradiated with microwaves (2.45 GHz) at an output of 500 W under an atmospheric pressure condition in an atmosphere having a partial pressure of oxygen and nitrogen of 1: 1. The microwave irradiation was held at 200 ° C. for 15 minutes while adjusting the electromagnetic wave output.

  By irradiating the microwave, the semiconductor precursor material area (thin film) 1 ′ is heated to a high temperature first in the gate electrode portion formed from ITO, and the semiconductor precursor material in the channel forming portion on the gate insulating layer Area 1 ′ (bicycloporphyrin compound) was also heated to the same extent as the electrode part, and thermally decomposed to be converted into a (TBP: tetrabenzoporphyrin copper complex) film, whereby semiconductor layer 1 was formed (thickness 50 nm, FIG. 3 (3)).

  Next, by depositing gold through a mask, the source electrode 2 and the drain electrode 3 were formed to produce a thin film transistor element. Each size was 10 μm wide, 50 μm long (channel width) and 50 nm thick, and the distance between the source electrode and the drain electrode (channel length) was 15 μm.

The thin film transistor manufactured by the above method showed p-type enhancement operation. An increase in drain current (transfer characteristics) was observed when the drain bias was −10 V and the gate bias was swept from +10 V to −40 V. The mobility estimated from the saturation region was 1.0 cm ² / Vs, the on / off ratio was 6 digits, and the thin film transistor was driven well and showed p-type enhancement operation.

  As a comparative example, after producing the ITO film, etching is performed by the photolithographic method so that the angle formed by the side of the electrode becomes the shape of Comparative 1 in FIG. Abnormal discharge was observed in the microwave irradiation process.

Example 2
A thin film transistor element was manufactured in the same manner as in Example 1 except that the semiconductor precursor material was changed to the following.

(Formation of semiconductor precursor thin film)
A 10 mass% aqueous solution in which indium nitrate, zinc nitrate, and gallium nitrate are mixed at a metal ratio of 1: 1: 1 (molar ratio) is ink-jet coated on the channel forming portion as an ink, and similarly treated at 150 ° C. for 10 minutes. And it dried and formed the semiconductor precursor material thin film 1 '(FIG. 3 (2)).

  By performing microwave irradiation under the same conditions as in Example 1, the semiconductor precursor material thin film 1 ′ was similarly converted into the semiconductor layer 1 by being thermally oxidized by the heat from the electrode part.

  Subsequently, the source electrode and the drain electrode were formed in the same manner as in Example 1 to manufacture a thin film transistor element.

The thin film transistor was driven well as in Example 1, the mobility was 5 cm ² / Vs or more, and the on / off ratio was 5 digits or more.

  As a comparative example, after producing the ITO film, etching is performed by the photolithographic method so that the angle formed by the side of the electrode becomes the shape of Comparative 1 in FIG. Abnormal discharge was observed in the microwave irradiation process.

Example 3
FIG. 4 shows a schematic sectional view of the manufacturing process.

  As a support 6, an ITO film is formed on a substrate using a glass substrate by sputtering, and then etched by a photolithographic method so that the angle formed by the sides of the electrode becomes an arc, and patterned to form a gate electrode. 4 (thickness 100 nm).

  Next, Aquamica NN110 (perhydropolysilazane / xylene solution: manufactured by AZ Electronic Material) was applied onto the substrate by spin coating (3000 rpm × 30 sec) and dried to form an insulating film precursor material layer 5 ′ (thickness 200 nm, FIG. 4 (1)).

  Microwave irradiation was performed under the same conditions as in Example 1. That is, microwaves (2.45 GHz) were irradiated with an output of 500 W under an atmospheric pressure condition in an atmosphere having a partial pressure of oxygen and nitrogen of 1: 1. Microwave irradiation was performed for 3 cycles with 1 cycle being 90 sec.

  The adjacent insulating film precursor material layer 5 ′ was subjected to heat treatment (firing) due to the heat generation of the ITO of the gate electrode, and became a silica glass film to form an insulating layer (FIG. 4 (2)).

(Formation of semiconductor precursor thin film)
Next, an ink was applied to the channel forming portion by ink coating on the insulating film as a 10% by mass aqueous solution in which indium nitrate, zinc nitrate, and gallium nitrate were mixed at a metal ratio of 1: 1: 1 (molar ratio). Then, it was treated at 150 ° C. for 10 minutes and dried to form a semiconductor precursor material area (thin film) 1 ′ (FIG. 4 (3)).

  Next, by performing microwave irradiation under the same conditions as in Example 2, similarly, the semiconductor precursor material area (thin film) 1 ′ was thermally oxidized by the heat from the electrode portion and converted into the semiconductor layer 1 (see FIG. 4 (4)).

  Next, the source electrode 2 and the drain electrode 3 were formed in the same manner as in Example 1 to form a thin film transistor element.

The thin film transistor was driven well as in Example 1, the mobility was 5 cm ² / Vs or more, and the on / off ratio was 5 digits or more.

  As a comparative example, after producing the ITO film, etching is performed by the photolithographic method so that the angle formed by the side of the electrode becomes the shape of Comparative 1 in FIG. Abnormal discharge was observed in the microwave irradiation process.

Example 4
A thin film transistor element was manufactured in the same manner as in Example 3 except that the insulating layer was replaced with the following polymer insulating film.

(Insulating film precursor material layer)
As in Example 3, spin-coating of thermosetting polyimide (CT4112 manufactured by Kyocera Chemical Co., Ltd.) at 4500 rpm × 20 sec (300 nm) on a substrate on which a gate electrode having an arc shape formed by the sides of the electrode was formed, thickness 200 nm An insulating film precursor material layer 5 'was formed.

  Next, microwave irradiation was performed under the same conditions as in Example 3. The insulating film precursor material layer 5 ′ was cured by heat from the electrode portion and converted to the insulating film 5 made of a polyimide film (FIG. 4 (2)).

  Next, the semiconductor layer 1, the source electrode 2, and the drain electrode 3 were formed in the same manner as in Example 3 to produce a thin film transistor element.

The formed thin film transistor was driven well as in Example 1, the mobility was 10 cm ² / Vs or more, and the on / off ratio was 5 digits.

  As a comparative example, after producing the ITO film, etching is performed by the photolithographic method so that the angle formed by the side of the electrode becomes the shape of Comparative 1 in FIG. Abnormal discharge was observed in the microwave irradiation process.

Example 5
A thin film transistor element was manufactured in the same manner as in Example 2 (FIG. 8 (1)).

  A semiconductor protective layer precursor material film 7 ′ was formed on the formed semiconductor layer 1 made of oxide by applying an uncured PVP aqueous solution having the following composition by an inkjet method (FIG. 8 (2)).

(Uncured PVP solution)
10% by mass of poly (4-vinylphenol) Aldrich
Cross-linking agent * 5% by mass
2-acetoxy-1-methoxypropane 85% by mass
* Crosslinking agent: Poly (melamine-co-formaldehyde), 84 mass% 1-butanol solution of methylated (manufactured by Aldrich)
Next, microwave irradiation was performed. That is, microwaves (2.45 GHz) were irradiated with an output of 500 W under an atmospheric pressure condition in an atmosphere having a partial pressure of oxygen and nitrogen of 1: 1. The microwave irradiation was held at 200 ° C. for 120 minutes while adjusting the electromagnetic wave output.

  The semiconductor protective layer precursor material film 7 ′ was cured when irradiated with microwaves, and a protective film 7 made of PVP was formed on the device (FIG. 8 (3)).

  It was shown that the method of the present invention can be applied to the formation of a protective film of a thin film transistor element.

  As a comparative example, after producing the ITO film, etching is performed by the photolithographic method so that the angle formed by the side of the electrode becomes the shape of Comparative 1 in FIG. Abnormal discharge was observed in the microwave irradiation process.

Example 6
Manufacturing Example of Bottom Gate / Top Contact Thin Film Transistor FIG. 9 is a schematic sectional view showing a manufacturing process.

  As in the third embodiment, the support 6 is a glass substrate, and the gate electrode 4 having a circular arc formed by the sides of the electrode on the substrate is used. Similarly, the insulating film precursor material layer 5 is formed using AQUAMICA NN110. 'Was formed (thickness 200 nm, (Fig. 9 (1)).

  After drying, a 10% by mass aqueous solution in which indium nitrate, zinc nitrate, and gallium nitrate were mixed at a metal ratio of 1: 1: 1 (molar ratio) was ink-jet coated on the channel forming portion as an ink, and similarly 150 The semiconductor precursor material thin film 1 ′ was formed by treatment at 10 ° C. for 10 minutes and drying (FIG. 9 (2)).

  Next, the substrate on which the insulating film precursor material layer 5 ′ and the semiconductor precursor material thin film 1 ′ were formed was irradiated with microwaves. That is, microwaves (2.45 GHz) were irradiated with an output of 500 W under an atmospheric pressure condition in an atmosphere having a partial pressure of oxygen and nitrogen of 1: 1. Microwave irradiation was performed for 4 cycles, with one cycle being 90 sec. The insulating film precursor material layer 5 ′ and the semiconductor precursor material thin film 1 ′ were simultaneously converted into the insulating layer 5 made of silicon oxide and the semiconductor layer 1, respectively.

  Next, in the same manner as in Example 1, a source electrode and a drain electrode were formed by gold vapor deposition to produce a thin film transistor element.

  Each of the source electrode and the drain electrode has a width of 10 μm, a length of 50 μm (channel width), a thickness of 50 nm, and a channel length of 15 μm.

The formed thin film transistor element has a mobility of 5 cm ² / Vs or more and an on / off ratio of 5 digits or more, so that it is driven well and conversion into an insulating layer and a semiconductor layer is performed.

  As a comparative example, in the case where the gate electrode was processed so that the angle formed by the sides of the electrode was the shape of Comparative 1 in FIG. 1, abnormal discharge was observed in the subsequent microwave irradiation process.

Example 7
Similarly, a thin film transistor element having a bottom gate / top contact configuration was fabricated.

  FIG. 10 is a schematic sectional view showing the manufacturing process.

  A glass substrate is used as the support 6, the substrate temperature is kept at 100 ° C. on the substrate, and gold nanoparticle ink (prepared by a method according to the method described in JP-A No. 11-80647) is used as an electrode material precursor. The electrode precursor thin film 4 ′ having a circular arc formed by the sides of the electrode precursor thin film was formed (thickness: 100 nm, FIG. 10 (1)).

  Next, the corner formed by the side of the electromagnetic wave absorbing layer by the inkjet method is similarly arcuately formed on the (gate) electrode precursor thin film 4 ′ using ITO nano-particle ink (Chikai Kasei NanoTek Slurry ITO (toluene)). Then, an electromagnetic wave absorption layer 4 ″ made of ITO fine particles was formed by patterning (thickness 50 nm, FIG. 10 (2)).

  Next, an insulating film precursor material layer 5 ′ is formed using aquamica NN110 (thickness 200 nm) in the same manner as in Example 6, and after drying, a semiconductor precursor in which In, Zn, and Ga salts are mixed in the channel formation portion. The material thin film 1 ′ is formed by patterning by the ink jet method, and the electrode precursor thin film 4 having an arc-shaped corner formed by the ink jet method using the ITO fine particle nano ink according to the source electrode and drain electrode patterns is formed. 'Was formed (FIG. 10 (3)).

  Next, microwave irradiation was performed on the substrate on which the electrode precursor thin film 4 ′ electromagnetic wave absorbing layer 4 ″ insulating film precursor material layer 5 ′ semiconductor precursor material thin film 1 ′ was formed. In a 1: 1 atmosphere, microwaves (2.45 GHz) were irradiated at an output of 500 W under atmospheric pressure conditions, and microwave irradiation was performed for 4 cycles, with one cycle being 90 sec.

  The electromagnetic wave absorbing layer 4 ″ (gate electrode) and the electrode precursor thin film 4 ′ (source and drain electrodes) made of ITO generate heat by absorption of microwaves, and the electrode precursor thin film 4 ′ insulating film precursor material layer 5 ′. The semiconductor precursor material thin film 1 ′ and the electrode precursor thin film 4 ′ were simultaneously converted into the gate electrode, the gate insulating layer 5, the semiconductor layer 1, the source electrode 2 and the drain electrode 3, respectively, to form a thin film transistor element (FIG. 10 ( 4)).

The manufactured thin film transistor element has a mobility of 5 cm ² / Vs or more, an on / off ratio of 5 digits or more, and is driven well, and it can be seen that conversion into an electrode, an insulating layer, and a semiconductor layer has been performed. .

  As a comparative example, the corners formed by the sides of the electrode precursor thin film, the corners formed by the sides of the electromagnetic wave absorption layer, and the corners formed by the sides of the electrode precursor thin film are processed so as to have the shape of comparison 1 in FIG. In the subsequent microwave irradiation process, abnormal discharge was observed.

Example 8
A thin film transistor element having a top gate / bottom contact configuration was fabricated.

  FIG. 11 is a schematic sectional view showing the manufacturing process.

  As the support 6, a source electrode 2 having four angles of 135 ° formed by electrode sides is formed on a glass substrate by gold vapor deposition and patterning, and four angles of 135 ° formed by electrode sides are formed. A drain electrode 3 having a thickness of 50 nm was manufactured (thickness 50 nm, FIG. 11 (1)).

  Next, the semiconductor precursor material thin film 1 ′ is a 10 mass% aqueous solution in which indium nitrate, zinc nitrate, and gallium nitrate are mixed at a metal ratio of 1: 1: 1 (molar ratio) as an ink, and the source and drain electrodes An ink-jet coating was applied to the channel forming part, and it was formed by treatment at 150 ° C. for 10 minutes and drying (thickness 50 nm, FIG. 11 (2)).

  Next, an insulating film precursor material layer 5 ′ was formed by ink jet coating using Aquamica NN110 (thickness 200 nm, FIG. 11 (3)).

  Next, using ITO nano-particle ink (CiC Kasei NanoTek Slurry ITO (toluene)), patterning like a gate electrode by an ink-jet method and electrodes having four angles of 135 ° formed by the sides of the electrode precursor thin film A precursor thin film 4 ′ was formed (thickness 100 nm, FIG. 11 (4)).

  When the microwave irradiation was performed in the same manner as in Example 7, the semiconductor precursor material thin film 1 ′, the insulating film precursor material layer 5 ′, and the electrode precursor thin film 4 ′ (gate electrode) were formed as a semiconductor layer and a gate insulating layer, respectively. At the same time, it was converted into a gate electrode to form a thin film transistor element (FIG. 11 (5)).

The manufactured thin film transistor element has a mobility of 5 cm ² / Vs or more, an on / off ratio of 5 digits or more, and is driven well, and conversion into an electrode, an insulating layer, and a semiconductor layer is performed. .

  As a comparative example, the corner formed by the sides of the source electrode, the corner formed by the sides of the drain electrode, and the corner formed by the sides of the electrode precursor thin film are processed in the shape of Comparative 1 in FIG. In the microwave irradiation process, abnormal discharge was observed.

Example 9
Similarly, a thin film transistor element having a top gate / bottom contact configuration was fabricated.

  FIG. 12 shows a schematic cross-sectional view of the manufacturing process.

A polyethylene naphthalate film (thickness: 200 μm) was used as the substrate 6, and first, a corona discharge treatment was performed thereon under the condition of 50 W / m ² / min. Thereafter, a heat insulating layer 8 was formed to improve adhesion as follows.

(Formation of heat insulation layer)
A silicon oxide film having a thickness of 300 nm was continuously provided by the atmospheric pressure plasma CVD method under the following conditions, and these layers were used as the heat insulating layer 8 (FIG. 12 (1)). As the atmospheric pressure plasma processing apparatus, an apparatus according to FIG. 6 described in JP 2003-303520 A was used.

(Used gas)
Inert gas: helium 98.25% by volume
Reactive gas: oxygen gas 1.5 volume%
Reactive gas: Tetraethoxysilane vapor (bubbled with helium gas) 0.25% by volume
(Discharge conditions)
High frequency power supply: 13.56 MHz
Discharge output: 10 W / cm ²
(Electrode condition)
The electrode is coated with 1 mm of alumina by ceramic spraying on a stainless steel jacket roll base material having cooling means with cooling water, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried, and then sealed by ultraviolet irradiation. This is a roll electrode having a dielectric (relative permittivity of 10) that has been subjected to hole treatment and has a smooth surface and an Rmax of 5 μm, and is grounded. On the other hand, as the application electrode, a hollow rectangular stainless steel pipe was coated with the same dielectric as described above under the same conditions.

  Next, on this heat insulating layer, as in Example 8, a source electrode having four corners formed by the sides of the electrode having a 135 ° angle and a drain having four corners formed by the sides of the electrode having a 135 ° angle are formed. Electrode (gold vapor deposition), semiconductor material precursor thin film 1 ', insulating film precursor material layer 5', four patterns with a 135 ° angle formed by sides of the electrode precursor thin film by patterning like a gate electrode with ITO fine particle ink The electrode precursor thin film 4 ′ having corners was sequentially formed (FIG. 12 (2)).

  When microwave irradiation was carried out in the same manner as in Example 7, the semiconductor precursor material thin film 1 ′, the insulating film precursor material layer 5 ′, and the electrode precursor thin film 4 ′ (gate electrode) were formed in the semiconductor layer 1 and the gate insulation, respectively. The thin film transistor element was formed by simultaneously converting into the layer 5 and the gate electrode 4.

  FIG. 12 (4) shows the cross-sectional view of the element and the thickness of each layer. Since this element has a heat insulation layer thickness of 300 nm, the shortest distance (l) from the heat source to the substrate is 450 nm, and the longest distance from the heat source to the precursor. Since (D) is 15 μm (approximately equivalent to the channel length (c = 15 μm)), the shortest distance from the heat source to the resin substrate / the longest distance from the heat source to the precursor = 1 / 33.3.

The manufactured thin film transistor element has a mobility of 5 cm ² / Vs or more and an on / off ratio of 5 digits or more, which is driven well and shows that the conversion to the electrode, the insulating layer, and the semiconductor layer has been performed. It is.

  As a comparative example, the corner formed by the sides of the source electrode, the corner formed by the sides of the drain electrode, and the corner formed by the sides of the electrode precursor thin film are processed in the shape of Comparative 1 in FIG. In the microwave irradiation process, abnormal discharge was observed.

Example 10
Here, an application example to an organic EL element is shown.

  In the same manner as in Example 9, a heat insulating layer 8 made of silicon oxide was produced on a polyethylene naphthalate film as a support 6 by an atmospheric pressure plasma CVD method (FIG. 13 (1)).

  Next, an ITO thin film was produced by sputtering to form an anode 11 having a circular arc formed by the sides of the anode (thickness 50 nm, FIG. 13 (2)).

  Further, a hole injection layer 12 and a hole transport layer 13 having the following composition were applied (FIG. 13 (3)).

Hole Injecting Layer Poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) diluted to 70% with pure water is spin-coated at 3000 rpm for 30 seconds. After film formation by the method, the film was dried at 200 ° C. for 1 hour to provide a 20 nm-thick hole injection layer.

Hole transport layer The sample was transferred to a nitrogen atmosphere, and a solution of 50 mg of the hole transport material 1 dissolved in 10 ml of toluene was formed on the hole transport layer by spin coating at 1500 rpm for 30 seconds. A hole transport layer having a thickness of about 20 nm was formed.

  Next, microwaves (2.45 GHz) were irradiated with an output of 500 W under a nitrogen atmosphere under atmospheric pressure conditions. Microwave irradiation was performed for 3 cycles with 1 cycle being 90 sec. In the hole transport layer, the hole transport material 1 having a crosslinking group was heated to 100 to 150 ° C. and crosslinked (thermosetting) to form a network polymer and insolubilized (FIG. 13 (4)). No dissolution or the like occurred when the following light emitting layer and electron transport layer were applied.

  Next, a film prepared by dissolving 100 mg of the following compound 1-1 and 10 mg of the following Ir-15 in 10 ml of toluene on the hole transport layer 13 was formed by a spin coating method at 1000 rpm for 30 seconds. It vacuum-dried at 120 degreeC for 1 hour, and was set as the light emitting layer with a film thickness of about 50 nm.

  Next, a solution obtained by dissolving 50 mg of the electron transport material 1 in 10 ml of 1-butanol was formed on this light emitting layer by spin coating under a condition of 5000 rpm for 30 seconds. It vacuum-dried at 60 degreeC for 1 hour, and was set as the electron carrying layer with a film thickness of about 15 nm.

Subsequently, this substrate is fixed to a substrate holder of a vacuum deposition apparatus, the vacuum chamber is decompressed to 4 × 10 ⁻⁴ Pa, lithium fluoride 1.0 nm is deposited as a cathode buffer layer, and aluminum 110 nm is deposited as a cathode to form a cathode. Then, an organic EL element was produced.

  When this organic EL element was energized, almost predetermined light emission was obtained. Separately, after forming the hole transport layer, it was irradiated with ultraviolet light for 180 seconds in a nitrogen atmosphere, and compared with the sample subjected to photopolymerization / crosslinking, There was no difference in light emission luminance and device life. It can be seen that by microwave irradiation, the hole transport layer was sufficiently cross-linked and the interface of the layer was not disturbed, and a cross-linked hole transport layer was formed.

  As a comparative example, an ITO thin film was fabricated by sputtering, and the anode was processed so that the angle formed by the sides of the anode became the shape of Comparative 1 in FIG. It was observed.

Example 11
Next, an example used for the structure of a thin film transistor circuit is shown.

  FIG. 14 shows a pixel unit circuit configuration of the manufactured transistor circuit together with an equivalent circuit diagram thereof. The transistor circuit includes two transistors, a switching transistor (Sw-TFT) and a driving transistor (D-TFT), a capacitor Cs, a bus line B (Vscan, Vdata, Vss), a display electrode 28, and the like, and a display element (OLED). Also, the wiring portion (Vk) after this is not shown.

  Hereinafter, an example of manufacturing the thin film transistor circuit (pixel unit) shown in FIG. 14 will be described with reference to schematic plan views and cross-sectional views of FIGS. In addition, it shows about manufacture to the display electrode except a display element (OLED) part.

  First, an ITO thin film (100 nm) pattern was formed on a glass substrate by sputtering so as to constitute a gate electrode, and subsequently, using a photoresist, the corners formed by the sides of the electrode were formed in an arc shape. The obtained gate electrode 22 (ITO pattern) is shown in FIG. This ITO pattern generates heat by microwave irradiation and plays a role of a heater in semiconductor formation.

  Next, after an aluminum film having a thickness of 300 nm is formed on one surface by sputtering, etching is performed by photolithography so that the angle formed by the bus lines B (Vscan, Vcap) and the sides of the electrodes becomes an arc shape. In addition, the storage capacitor electrode Cs1 and the formation region of the through hole TH connected to the gate electrode 22 of the driving transistor are formed so that the angle formed by the sides of the electrode becomes an arc shape (FIG. 15B).

  Next, the gate insulating film 23 was formed leaving the through hole TH (also serving as a capacitor capacitor insulating film). As for the gate insulating film 23, silicon oxide having a thickness of 200 nm is formed by an atmospheric pressure plasma CVD method (the atmospheric pressure plasma processing apparatus uses an apparatus according to FIG. 6 described in Japanese Patent Laid-Open No. 2003-303520) ( FIG. 15 (3)).

  On the gate insulating film, a 10% by mass aqueous solution in which indium nitrate, zinc nitrate, and gallium nitrate were mixed at a metal ratio of 1: 1: 1 (molar ratio) was applied, and dried at 150 ° C. for 10 minutes to be a precursor. A material thin film 26 'was formed (FIG. 15 (4)).

  After forming the precursor material thin film 26 ', microwave irradiation was performed. That is, microwaves (2.45 GHz) were irradiated with an output of 500 W under an atmospheric pressure condition in an atmosphere having a partial pressure of oxygen and nitrogen of 1: 1.

  Microwave irradiation was performed for 4 cycles, with one cycle being 90 sec. As a result, the precursor material thin film was converted into the oxide semiconductor layer 26 in accordance with the gate electrode 23 (ITO) pattern by heat generation due to the microwave absorption of ITO. The substrate was rinsed thoroughly with distilled water to wash away unconverted areas of the precursor material film 26 '. An oxide semiconductor layer 26 was formed on the gate insulating film so as to face the gate electrode (FIG. 16 (1)).

  As the next step, a channel protective film 27 was formed on the semiconductor pattern.

  That is, a piezo method using a solution obtained by dissolving the following composition in Isopar E ″ (isoparaffinic hydrocarbon, manufactured by Exxon Chemical Co., Ltd.) as an aqueous dispersion and diluting to a solid concentration of 10.3% by mass as an ink. The ink was ejected according to a pattern by the inkjet method, heated (100 ° C.), and dried to form a protective film 7 having a thickness of 0.4 μm (FIG. 16B).

(Composition)
α, ω-divinylpolydimethylsiloxane (molecular weight about 60,000) 100 parts HMS-501 (both terminal methyl (methylhydrogensiloxane) (dimethylsiloxane) copolymer, SiH group number / molecular weight = 0.69 mol / g, Chisso (Made by Co., Ltd.)
7 parts Vinyltris (methylethylketoxyimino) silane 3 parts SRX-212 (platinum catalyst, manufactured by Toray Dow Corning Silicone Co., Ltd.) 5 parts Next, chromium is vapor-deposited through a mask so that the source electrode 24 and the drain electrode 25 Further, the counter electrode Cs2 of the capacitor, the data or bus line B (Vdata, Vss), and the pixel electrode 28 were formed (FIG. 16 (3)). The through hole portion was also deposited, and the switching transistor and the driving transistor were electrically connected.

  Next, the pixel electrode 28 portion was left and sealed with a sealing film S made of an ethylene-vinyl alcohol copolymer. That is, isopropyl alcohol was added to an ethylene-vinyl alcohol copolymer having an ethylene content of 29 mol%, a saponification degree of 99.5 mol%, and a polymerization degree of 1000, and heated to 80 ° C. to prepare a solution having a concentration of about 5%. Then, a sealing film (thickness 5 μm) was formed by coating by patterning using a photoresist (FIG. 16 (4)).

  By incorporating an organic EL element (OLED) as a display element into the produced TFT sheet, it could be driven satisfactorily.

  As a comparative example, the corner formed by the side of the gate electrode of the switching transistor, the corner formed by the side of the electrode for the storage capacitor, and the corner formed by the side of the gate electrode of the driving transistor are in the shape of comparison 1 in FIG. In the processed product, abnormal discharge was observed in the subsequent microwave irradiation process.

It is a figure which shows the planar shape of the conventional electrode. It is a figure which shows the planar shape of the electrode which concerns on this invention. It is a schematic sectional drawing which shows the 1st aspect of this invention which converts the heat conversion material on this into a semiconductor layer by irradiating electromagnetic waves by making an electrode pattern (area) into a heat source. It is a schematic sectional drawing which shows the 2nd aspect of this invention which converts the heat conversion material on this into an insulating layer by irradiating electromagnetic waves by making an electrode pattern (area) into a heat source. It is a figure which shows the relationship between the distance of a heat source area and a board | substrate, and the distance of a heat source area and the functional layer precursor area | region which is heat-converted. It is a figure which shows the typical structure of a film transistor element. 1 is a schematic equivalent circuit diagram of an example of a thin film transistor sheet 10 which is an electronic device in which a plurality of thin film transistor elements are arranged. It is a figure which shows the manufacturing process of Example 5 with a schematic sectional drawing. It is a figure which shows the manufacturing process of Example 6 with a schematic sectional drawing. It is a figure which shows the manufacturing process of Example 7 with a schematic sectional drawing. It is a figure which shows the manufacturing process of Example 8 by schematic sectional drawing. It is a figure which shows the manufacturing process of Example 9 with a schematic sectional drawing. It is a figure which shows the example of application to the organic EL element of this invention. It is a figure which shows the circuit structure of the pixel unit of the produced transistor circuit, and its equivalent circuit schematic. It is the schematic which shows the preparation processes of a thin-film transistor circuit per pixel. It is the schematic which shows the preparation processes of a thin-film transistor circuit per pixel.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor layer 2 Source electrode 3 Drain electrode 4 Gate electrode 5 Gate insulating layer 10 Thin-film transistor sheet 11 Gate bus line 12 Source bus line 14 Thin-film transistor element 15 Storage capacitor 16 Output element 17 Vertical drive circuit 18 Horizontal drive circuit

Claims (25)

An area having an electrode on a substrate and containing heat conversion material or heat conversion material in at least one part, and a substance or electromagnetic wave having electromagnetic wave absorption ability adjacent to or adjacent to the heat conversion material or area containing heat conversion material In the method of manufacturing an electronic device in which an area including an absorptive substance is disposed, irradiated with an electromagnetic wave, and heat conversion material is converted into a functional material by heat generated by the electromagnetic wave absorptive substance, A method for manufacturing an electronic device, characterized in that all the angles formed by the sides are larger than 90 ° and smaller than 180 °, or a curved surface. The method for manufacturing an electronic device according to claim 1, wherein the substance having electromagnetic wave absorbing ability is a metal oxide. The method of manufacturing an electronic device according to claim 1, wherein the substance having electromagnetic wave absorbing ability is a conductor. 4. The method for manufacturing an electronic device according to claim 2, wherein the metal oxide includes at least one of In, Sn, and Zn. The method of manufacturing an electronic device according to claim 1, wherein the electronic device is a transistor element. The method for manufacturing an electronic device according to claim 1, wherein the heat conversion material is a semiconductor precursor material. The method for manufacturing an electronic device according to claim 1, wherein the heat conversion material is an insulating film precursor material. The method for manufacturing an electronic device according to claim 1, wherein the heat conversion material is a protective film precursor material. The method for manufacturing an electronic device according to claim 1, wherein the heat conversion material is an electrode precursor material. The method of manufacturing an electronic device according to claim 9, wherein the electrode precursor material contains a metal and is adjacent to an area containing a substance having electromagnetic wave absorbing ability or a substance having electromagnetic wave absorbing ability. The method of manufacturing an electronic device according to claim 6, wherein the semiconductor precursor material is a metal oxide semiconductor precursor and is converted into a metal oxide semiconductor. The method of manufacturing an electronic device according to claim 11, wherein the metal oxide semiconductor precursor contains at least one of In, Zn, and Sn. The method for manufacturing an electronic device according to claim 11 or 12, wherein the metal oxide semiconductor precursor contains Ga or Al. The method of manufacturing an electronic device according to claim 6, wherein the semiconductor precursor material is an organic semiconductor precursor and is converted into an organic semiconductor. After forming an electrode containing a substance having electromagnetic wave absorbing ability and at least two functional layer precursor areas among an insulating film precursor area, a semiconductor precursor area, and a protective film precursor area, an electromagnetic wave is irradiated to form a functional layer precursor. The method for manufacturing an electronic device according to claim 1, wherein the functional layer is formed by simultaneously heating the body layer area. After forming an electrode precursor area containing an electromagnetic wave absorbing substance or an electromagnetic wave absorbing substance, and at least one functional layer precursor area among an insulating film precursor area, a semiconductor precursor area, and a protective film precursor area The electronic device according to any one of claims 1 to 14, wherein the electrode and the functional layer are simultaneously formed by irradiating electromagnetic waves and simultaneously heating the electrode precursor area and the functional layer precursor area. Production method. The transistor element according to any one of claims 6 to 16, wherein the transistor element has a bottom gate structure, and the gate electrode is formed of an area including a substance having an electromagnetic wave absorbing ability or a substance having an electromagnetic wave absorbing ability. Electronic device manufacturing method. 17. The device according to claim 5, wherein the transistor element has a bottom contact structure, and the gate electrode includes an area containing a substance having an electromagnetic wave absorbing ability or a substance having an electromagnetic wave absorbing ability. Electronic device manufacturing method. The transistor element according to any one of claims 5 to 16, wherein the transistor element has a top gate structure, and the gate electrode includes an area containing a substance having an electromagnetic wave absorbing ability or a substance having an electromagnetic wave absorbing ability. Electronic device manufacturing method. The method for manufacturing an electronic device according to any one of claims 1 to 19, wherein the electromagnetic wave is a microwave (frequency: 0.3 to 50 GHz). 21. At least one layer of an electrode precursor material, a semiconductor precursor material, an insulator precursor material, and a protective film precursor material of the transistor element is formed by coating. The manufacturing method of the electronic device of description. The substrate temperature of an electronic device is 50-200 degreeC, and coating-film surface temperature is 200-600 degreeC, The manufacturing method of the electronic device of any one of Claims 1-21 characterized by the above-mentioned. The method for manufacturing an electronic device according to claim 1, wherein the substrate is a resin substrate. The shortest distance between the area (heat source area) containing an electromagnetic wave absorbing substance or an electromagnetic wave absorbing substance and the base of the electronic device is on the functional layer precursor area side where the electromagnetic wave is absorbed and heat is generated. The electronic device according to any one of claims 1 to 23, which is 1/200 to 10 times the longest distance between the boundary surface and the entire boundary of the functional layer precursor area to be heat-converted. Production method. An electronic device manufactured by the method for manufacturing an electronic device according to claim 1.

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