JP2006021491A - LAMINATED STRUCTURE, OPTICAL ELEMENT, DISPLAY ELEMENT, OPERATION ELEMENT USING LAMINATED STRUCTURE, AND METHOD FOR PRODUCING THEM - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated structure which allows application of a low-cost and high material use efficiency process like a printing process and formation of a simple and fine pattern and has a function with a high value added in addition to the pattern formation, and optics using this laminated structure, a display element, an arithmetic element and a method for manufacturing these elements. <P>SOLUTION: The laminated structure 1 has an insulating material layer 2 laminated on at least a first conductive material 7 and a second conductive material 5 laminated on the insulating material layer 2. The insulating material layer 2 is constituted of an insulating wet changing layer possessing an insulating function and a critical surface tension changing function to work by energy application. The second conductive material 5 is structurally formed in a region where a high surface energy part 3 of the insulating wet changing layer is found. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a laminated structure in which a second conductive material is laminated on an insulating material layer on a first conductive material, an optical element using the laminated structure, a display element, an arithmetic element, and these It relates to a manufacturing method.

  As electronic elements such as arithmetic elements are required to be highly integrated like VLSI and ULSI in recent years, the importance of multi-layered elements and fine wiring technology has increased. An example of the arithmetic circuit is shown in FIG. P-ch and n-ch in FIG. 20 indicate a transistor as an arithmetic element using a hole transport material and a transistor as an arithmetic element using an electron transport material, respectively. This is an example of a NOT operation circuit, but other operation circuits such as OR, NAND, NOR, and XOR are integrated / connected via an interlayer insulating film as illustrated in FIG. In addition, a highly integrated arithmetic element 70 is configured by connecting a fine wiring electrode 72 on the interlayer insulating film 71. FIG. 21B shows a configuration example of the transistor 60 as an arithmetic element. In this example, the gate electrode 62 is provided on one surface of the gate insulating film 61, and the semiconductor 65 is provided between the source electrode 63 and the drain electrode 64 on the other surface. The arithmetic element 70 is configured by stacking a plurality of these transistors 60.

  Like the display device 80 shown in FIG. 22, an active element 60 such as a transistor is arranged on a substrate 81 on the non-display side to form an electronic element array 86, and a pixel electrode 81 is formed on the interlayer insulating film 82. When a voltage is applied between the pixel electrode 81 and a transparent electrode (transparent dielectric layer) 73 provided on the substrate 85 on the display side, the display element 84 displays an image. In order to perform high-definition display on such a display element 84, the pixel electrode 81 needs to be finely formed on the interlayer insulating film 82. As can be seen from FIGS. 21 and 22, the interlayer insulating film 82 is formed not only on the electrode material but also on the semiconductor material layer 65 when the transistor 60 is provided.

In recent years, an element using an organic material as a semiconductor material has attracted attention because of its merit in manufacturing such as cost reduction and ease of enlargement, and the possibility of a function not found in an inorganic material. For example, Patent Document 1 proposes a field effect transistor using an organic semiconductor material whose carrier mobility is changed by a physical external stimulus such as light or heat. Patent Document 2 proposes the use of SiO2 as an interlayer insulating film material. In general, when an electrode wiring pattern is finely formed on an interlayer insulating film, a photolithography method is generally used. The process is as shown in Process A below.
(1) A photoresist layer is applied on a substrate having a thin film layer (resist application).
(2) The solvent is removed by heating (pre-baking).
(3) Irradiate ultraviolet light through a mask (exposure).
(4) The resist in the exposed area is removed with an alkaline solution (development).
(5) The unexposed portion (pattern portion) resist is cured by heating (post-bake).
(6) Immersion in an etchant or exposure to an etching gas to remove the thin film layer where there is no resist (etching).
(7) The resist is removed with an alkaline solution or oxygen radical (resist stripping).

  However, since such a long process is required, there is a problem that the manufacturing cost is increased. In order to solve this problem, Patent Document 3 discloses that an organosiloxane is applied to an electrode forming surface, only a portion where an electrode is wired is made hydrophilic by UV exposure, and a conductive ink such as an ultrafine gold colloid solution or a PEDOT solution is used here. A method of applying the ink by inkjet is disclosed.

JP-A-7-86600 JP 05-036627 A JP-A-2002-261048

  In the field effect transistor described in Patent Document 1, an organic semiconductor material is used, and the organic semiconductor material may be dissolved in an organic solvent having a small polarity such as toluene, THF, xylene, or the like, and may be formed by coating. When the interlayer insulating film is formed by using this, there is a problem that the organic semiconductor material layer is damaged.

In Patent Document 2, since SiO ₂ having a high withstand voltage is used as an interlayer insulating film material, it is a highly reliable material as an interlayer insulating film, but generally needs to be formed by a vacuum film forming process such as sputtering. . In this case, there is a problem that the apparatus cost increases. Since this problem is the same when Si ₃ N ₄ , SiON, or the like is used, a material that can be formed by a coating process such as spin coating and has a high withstand voltage has been desired. In the interlayer insulating film, it is necessary to reduce the parasitic capacitance that causes wiring delay. Since this wiring delay causes a decrease in the operating frequency of an arithmetic element such as an LSI, a material having a relative dielectric constant smaller than SiO 2 (ε = less than 3.9) has been desired.

  In Patent Document 3, when the electrode formation surface is an interlayer insulating film, it is possible to finely form an electrode pattern by a simpler process than photolithography, but organosiloxane itself does not have an insulating function. For this reason, it is necessary to take the steps of coating the insulating material → coating the organosiloxane → exposure. In the current multilayer wiring, electrode wiring is performed in a structure of 5 to 6 layers. Therefore, if the number of manufacturing steps for manufacturing one layer is increased as much as possible, there is a problem that the entire manufacturing process is greatly increased. It was.

  INDUSTRIAL APPLICABILITY The present invention can be applied to a low cost and high material use efficiency method such as a printing method, can easily form a fine pattern, and has a high added value function other than pattern formation. An object of the present invention is to provide an optical element, a display element, an arithmetic element, and a manufacturing method thereof that are easy to manufacture using such a laminated structure and have high performance.

  In order to achieve the above object, the laminated structure according to the present invention includes an insulating material layer laminated on at least a first conductive material, and a second conductive material laminated thereon, so The insulating material layer is an insulating wetting change layer having an insulating function and a function of changing the critical surface tension by the application of energy, and the second conductive material is placed at a portion of the high surface energy portion of the insulating wetting change layer. It is characterized by being formed.

  In the laminated structure, the solvent used for forming the insulating wetting change layer may contain water and an organic solvent that can be dissolved at an arbitrary ratio.

  As the insulating wetting change layer, a low surface energy part and a high surface energy part are formed by energy irradiation, and the difference between the critical surface tension of the low surface energy part and the critical surface tension of the high surface energy part is 10 mN / m. It may be characterized by the above.

  The insulating wetting change layer is composed of two or more kinds of materials, and preferably has at least a first material whose critical surface tension is largely changed relatively by application of energy and a function other than the wettability change. And a second material.

  In the case where the insulating wetting change layer includes a first material and a second material, and the first material has a critical surface tension greatly changed by applying energy as compared with the second material, May be a material having high electrical insulation compared to the first material, a material having a low dielectric constant compared to the first material, or a material having a high dielectric constant compared to the first material. .

  In the laminated structure, the material whose critical surface tension greatly changes by applying energy is a polymer material containing a hydrophobic group in the side chain, and the polymer having a hydrophobic group in the side chain As the material, a polymer material containing polyimide is preferable. Application of energy for changing the critical surface tension is preferably ultraviolet irradiation. The laminated structure may be configured such that a part of the insulating wetting change layer is removed and the first and second conductive material layers are connected to each other at the removal portion.

  The method for producing a laminated structure according to the present invention includes a step of forming an insulating wetting change layer on at least a first conductive material layer, and applying energy to a part of the insulating wetting change layer to form a critical surface. Forming a pattern having different critical surface tensions consisting of a low surface energy part having a low tension and a high surface energy part having a high critical surface tension, and a liquid containing a second conductive material on the high surface on the pattern A step of forming an interlayer insulating film between the electrodes formed in two layers by being applied to the energy part is characterized. Even in this case, it is preferable to apply energy for changing the critical surface tension by ultraviolet irradiation.

  An electronic device according to the present invention is characterized in that each of the above laminated structures is provided as a constituent element. An electronic device according to the present invention is characterized in that a multilayer structure manufactured by the above-described method for manufacturing a multilayer structure is provided as a constituent element. In these electronic elements, a part of the insulating wetting change layer may be removed, and the first and second conductive material layers may be connected to each other at the removal portion.

  In the method for manufacturing an electronic device according to the present invention, the method of applying at least one of the liquids containing the first and second conductive materials to the surface of the material on which the wettability pattern is formed is a spin coating method or a dipping method. And any one of a blade coating method, a spray coating method, and an ink-jet method.

  A display element or an arithmetic element according to the present invention is characterized by using the electronic element.

  The method for manufacturing a display element according to the present invention is such that a method of applying at least one of the liquids containing the first and second conductive materials to the surface of the material on which the wettability pattern is formed is a spin coating method or a dipping method. It is characterized by being manufactured by any one of the blade coating method, the spray coating method and the ink jet method.

  In the method for manufacturing an arithmetic element according to the present invention, a method of applying at least one of the liquids containing the first and second conductive materials to the surface of the material on which the wettability pattern is formed is a spin coating method or a dipping method. It is characterized by being manufactured by any one of the blade coating method, the spray coating method and the ink jet method.

  According to the present invention, the insulating material layer is laminated on at least the first conductive material, and the second conductive material is laminated thereon, and the insulating material layer has an insulating function and energy. An insulating wetting change layer having a function of changing the critical surface tension by the application, and the second conductive material is formed at a portion of the high surface energy portion of the insulating wetting change layer. It is possible to provide a laminated structure in which a fine conductive layer pattern is formed on an insulating material layer on a conductive material by such a low cost and high material use efficiency method.

  According to the present invention, the step of forming an insulating wetting change layer on at least the first conductive material layer, and applying low energy to a part of this material, a low surface energy portion having a small critical surface tension. Forming a pattern having a different critical surface tension comprising a high surface energy part having a large critical surface tension, and applying a liquid containing a second conductive material to the high surface energy part on the pattern Thus, since the interlayer insulating film is formed between the electrodes formed in two layers, it is possible to provide an electronic device having a simple manufacturing process and a fine structure.

  According to the present invention, a method in which an electronic element, a display element, or an arithmetic element applies one of liquids containing at least first and second conductive materials to a material surface on which a wettability pattern is formed is a spin. Since it is manufactured by any of the coating method, dipping method, blade coating method, spray coating method or ink jet method, the device manufacturing time can be greatly shortened and a printing apparatus is not required, so that the manufacturing cost is greatly reduced. be able to.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of the principle configuration of the laminated structure 1 of the present embodiment. The laminated structure 1 of the present embodiment is configured as a base by laminating a wettability changing layer 2 as an insulating material layer on at least a first conductive material 7 provided on a substrate 6. . The wettability changing layer 2 is a layer made of a material whose critical surface tension changes with the application of energy. In this embodiment, at least two parts having different critical surface tensions are used as a high surface having a higher critical surface tension. It has an energy part 3 and a low surface energy part 4 with a smaller critical surface tension. Here, a gap between two high surface energy portions 3 in the illustrated example is set to a minute gap of about 1 to 5 μm, for example. In addition, conductive layers 5 are formed at portions of the high surface energy portion 3 with respect to the wettability changing layer 2. That is, in the laminated structure 1, the insulating material layer 2 is laminated on at least the first conductive material 7, and the second conductive material 5 is laminated thereon. The insulating wettability changing layer 2 having an insulating function and a function of changing the critical surface tension by applying energy, and the second conductive material 5 is placed at the site of the high surface energy portion 3 of the insulating wetting changeable layer 2. Is formed.

  The wettability changing layer 2 is a layer made of a material whose critical surface tension changes by applying energy such as heat, ultraviolet rays, electron beams, plasma, etc., and has a large change amount of the critical surface tension before and after energy application. preferable. In the case of such a material, by applying energy to a part of the wettability changing layer 2 and forming patterns having different critical surface tensions composed of the high surface energy part 3 and the low surface energy part 4, the conductive material can be obtained. Since the contained liquid easily adheres to the high surface energy part 3 (lyophilic) and hardly adheres to the low surface energy part 4 (lyophobic), the liquid containing the conductive material according to the pattern shape The conductive layer 5 is formed by selectively adhering to the high surface energy part 3 that is lyophilic and solidifying it.

  Here, the liquid wettability (adhesiveness) to the solid surface will be added. FIG. 2 is a schematic diagram when the droplet 12 is in an equilibrium state at the contact angle θ on the surface of the solid 11, and Young's formula (1) is established.

γS = γSL + γLcosθ (1)
Here, γS is the surface tension of the solid 11, γSL is the interface tension between the solid 11 and the liquid (droplet 12), and γL is the surface tension of the liquid (droplet 12).

  The surface tension is substantially synonymous with the surface energy and has exactly the same value. When cos θ = 1, θ = 0 °, and the liquid (droplet 12) is completely wetted. The value of γL at this time is γS−γSL, which is called the critical surface tension γC of the solid 11. γC plots the relationship between the surface tension of the liquid (droplet 12) and the contact angle using several types of liquid whose surface tension is known, and obtains the surface tension at which θ = 0 ° (cos θ = 1). (Zisman plot). The liquid (droplet 12) is easily wetted on the surface of the solid 11 having a large γC (lyophilic), and the liquid (droplet 12) is hardly wetted on the surface of the solid 11 having a small γC (lyophobic).

Here, it is easy to measure the contact angle θ by the droplet method. For the droplet method,
(A) A tangent method in which the reading microscope is directed to the droplet 12 and the cursor line in the microscope is aligned with the contact point of the droplet 12 to read the angle.
(B) The θ / 2 method obtained by doubling the angle of the cursor line when the cross cursor is aligned with the apex of the droplet 12 and one end is aligned with the point where the droplet 12 and the solid 11 sample contact each other.
(C) A three-point click method in which a droplet 12 is projected on a monitor screen, and one point (preferably a vertex) on the circumference and a contact point (two points) between the droplet 12 and the solid 11 sample are clicked and processed by a computer.
There is. The accuracy increases in the order of (a) → (b) → (c).

  FIG. 3 shows a Zisman plot of a non-UV-irradiated part and an UV-irradiated part using the material described later (Example 1) for the wettability changing layer 2. From the figure, it can be seen that the critical surface tension γC of the UV-irradiated part is about 24 mN / m, the critical surface tension γC ′ of the UV-irradiated part is about 45 mN / m, and the difference ΔγC is about 21 mN / m.

  In order to ensure that the liquid containing the conductive material adheres only to the high surface energy part 3 that is lyophilic according to the pattern shape of the high surface energy part 3 and the low surface energy part 4, the surface energy difference is large. In other words, the critical surface tension difference ΔγC needs to be large.

  Table 1 shows the wettability changing layer 2 made of various materials formed on a glass substrate, and the evaluation of selective adhesion of ΔγC and polyaniline (aqueous conductive polymer) between the energy-applied part and the non-applied part. is there. For selective adhesion, an aqueous polyaniline solution was dropped on an area including the boundary of the pattern consisting of the energy imparted part and the unapplied part, and after removing the excess solution, the presence or absence of polyaniline adhering to the unapplied part (pattern defect) was observed. . In Table 1, A: Marka Linker M (Maruzen Chemical), B: RN-1024 (Nissan Chemical), C: AG-7000 (Asahi Glass) D: Chemical formula of A after firing and chemical formula of Chemical Formula 7 described later Polyimide mixture represented.

  From Table 1, the difference (ΔγC) between the critical surface tension of the low surface energy portion 4 and the critical surface tension of the high surface energy portion 3 of the wettability changing layer 2 is preferably 10 mN / m or more, and 15 mN / m or more. It turns out that it is further desirable.

  That is, the present inventors apply energy such as ultraviolet rays to a part of the insulating wetting change layer 2 and provide a portion having different wettability (a portion having a different critical surface tension) to select a conductive layer thereon. In addition, it was confirmed that by using the laminated structure 1 configured as described above, it is possible to provide an electronic device having a simple manufacturing process and a fine structure. Is.

  Therefore, in order to ensure that the liquid containing the conductive material adheres only to the lyophilic high surface energy part 3 according to the pattern shape of the high surface energy part 3 and the low surface energy part 4, the surface energy difference is In other words, the difference in critical surface tension between these energy parts needs to be large, but by setting this difference to 10 mN / m or more, a liquid containing a conductive material can be reliably attached. it can.

  With the above configuration, a fine conductive layer pattern is formed on the insulating wetting change layer 2 (insulating material layer) on the conductive material 7 by a low cost and high material use efficiency method such as a printing method. The laminated structure 1 can be provided. In addition, the insulating wetting change layer 2 can be made of a low dielectric material or a high dielectric material depending on the application. When used as an interlayer insulating film, a low dielectric constant material is desirable in order to reduce parasitic capacitance that causes wiring delay. Further, in the case of forming a capacitor having a high electric capacity to be an electronic element, it is necessary to use a material having a high dielectric constant.

In the case of forming a film with the insulating wetting change layer 2, the solvent used for the film contains water and an organic solvent that can be dissolved at an arbitrary ratio. In this case, the insulating wetting change layer 2 is not damaged with respect to the material dissolved in the organic solvent having a low polarity, and a film can be formed thereon.
Solvents used in this embodiment include alcohol solvents such as ethanol, methanol and propanol, glycol solvents such as ethylene glycol, propylene glycol and diethylene glycol, cellosolve solvents such as 2-methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol. A solvent etc. are mentioned. In addition, the ratio of the solvent that can be dissolved in water and an arbitrary ratio to the total solvent for the insulating wettability changing material is preferably 30 vol% or more. More desirably, 90 vol% or more is desirable.

  The insulating wetting change layer 2 is made of two or more kinds of materials on the substrate 6 as shown in FIG. Therefore, by using materials having different characteristics, it is possible to give the insulating wetting change layer characteristics other than the wettability change. As an example of this, a material having a large change in wettability but having a problem in film forming property can be used, so that more materials can be selected. Specifically, when the change in wettability of the first material 13 indicated by white circle is larger but the cohesive force is strong, it is difficult to form a film. It becomes possible to produce the said wettability change layer 2 easily by mixing with the 2nd material 14 shown by.

  FIG. 5 to FIG. 9 show that the insulating wetting change layer 2 is composed of at least a first material 13 and a second material 14, and the first material 13 is compared with the second material 14 by applying energy to the critical surface. The second material 14 is made of a material having a function other than a change in wettability, and has a material distribution in the film thickness direction indicated by an arrow C. Is higher than the concentration of the second material 14, but any of them can be applied in the present invention.

  The structure shown in FIG. 5 can be manufactured by sequentially laminating the layer 14A made of the second material 14 after the layer 13A made of the first material 13 is made. As a manufacturing method, a vacuum process such as vacuum vapor deposition can be used, or a coating process using a solvent can be used.

  A process for obtaining the structure shown in FIG. 6 includes a method in which a solution in which the first material 13 and the second material 14 are mixed is applied to the substrate 6 and dried. This is because, when the polarity of the first material 13 is smaller than that of the second material 14 or when the molecular weight of the first material 13 is small, the first material 13 is evaporated before the solvent evaporates during drying. 13 moves to the surface side and forms a layer. When the coating process is used, the layer 13A made of the first material 13 and the layer 14A made of the second material 14 are often not clearly separated by the interface as shown in FIG. In the form, it is applicable if the concentration of the first material 13 in the outermost layer 2 </ b> A is higher than the concentration of the second material 14. As shown in FIGS. 7, 8, and 9, the first material 13 and the second material 14 may be mixed in a predetermined concentration distribution with respect to the film thickness direction C.

  When the insulating wetting change layer 3 is composed of three or more kinds of materials, it may have a laminated structure of three or more layers, and has a predetermined concentration distribution in the film thickness direction C without having a layer structure. The structure may be a mixture of materials.

  As shown in FIG. 10, the insulating wetting change layer 2 is composed of at least a first material 13 and a second material 24, and the first material 23 has energy compared to the second material 24. The second material 24 may be made of a material whose critical surface tension is greatly changed by the application, and which is higher in electrical insulation than the first material 13. In this case, it is possible to provide the laminated structure 1 that is excellent in electrical insulation and capable of forming a fine conductive layer pattern.

In the present embodiment, the second / first composition ratio of the second material 24 excellent in electrical insulation and the first material 13 whose critical surface tension greatly changes due to the application of energy is 50/50 by weight. ~ 99/1. As the weight ratio of the first material 13 increases, the insulating property of the insulating wetting change layer 2 becomes low and becomes unsuitable as an insulating layer of an electronic element. On the other hand, when the weight ratio of the second material 24 is increased, the change in wettability is reduced, so that the patterning of the conductive layer is not good. Therefore, the mixing ratio between the two is desirably 60/40 to 95/5, and more desirably 70/30 to 90/10. Moreover, it is preferable that the volume specific resistance value of the insulating wetting change layer 2 in this embodiment is about 1 × 10 ¹² Ω · cm or more.

  As shown in FIG. 11, the insulating wetting change layer 2 is composed of at least a first material 13 and a second material 34, and the first material 13 is applied with energy as compared with the second material 34. The material whose critical surface tension changes greatly, and the second material 34 is composed of a material having a lower dielectric constant than the first material 13. Accordingly, when the interlayer insulating film shown in FIGS. 21 and 22 is formed, it is possible to reduce the parasitic capacitance that causes the wiring delay. Since the wiring delay causes a reduction in the operating frequency of an arithmetic element such as an LSI, an arithmetic element having a high operating frequency can be manufactured by using the layer configuration as in this embodiment. The low dielectric constant in this embodiment refers to less than the relative dielectric constant (3.9) of SiO 2 that is generally used as an insulating film.

  As shown in FIG. 12, the insulating wetting change layer 2 includes at least a first material 13 and a second material 44, and the first material 13 is applied with energy compared to the second material 44. The second material 44 is made of a material having a high dielectric constant as compared with the first material 14. For this reason, it is possible to manufacture an electronic device 20 such as a high-capacitance capacitor having the electrode (first conductive material) 7 and the electrode (second conductive material) 5 above and below the insulating wetting change layer 2. It becomes possible. In this embodiment, the high dielectric constant refers to a relative dielectric constant of 8.5 or more of aluminum oxide used as a capacitor dielectric.

  In this embodiment, examples of the material whose critical surface tension is greatly changed by energy application include a polymer material containing a hydrophobic group in a side chain. For this reason, since the difference between the water-repellent part and the hydrophilic part is increased by the application of energy, it is possible to manufacture the laminated structure 1 on which fine electrode patterning is performed on the insulating wetting change layer 2.

  FIG. 13 shows a conceptual diagram of a polymer material containing a hydrophobic group in the side chain. As shown in this figure, there can be mentioned those in which a side chain R having a hydrophobic group is bonded to a main chain L having a skeleton such as polyimide or (meth) acrylate directly or via a bonding group (not shown). .

Examples of the hydrophobic group include groups having a terminal structure of —CF ₂ CH ₃ , —CF ₂ CF ₃ , —CF (CF ₃ ) ₂ , —C (CF ₃ ) ₃ , —CF ₂ H, —CFH _{2 and the} like. Can be mentioned. In order to facilitate the alignment of molecular chains, a group having a long carbon chain length is preferable, and a group having 4 or more carbon atoms is more preferable. Furthermore, a polyfluoroalkyl group in which two or more hydrogen atoms of the alkyl group are substituted with fluorine atoms (hereinafter referred to as “Rf group”) is preferable, and an Rf group having 4 to 20 carbon atoms is particularly preferable. Rf groups having 6 to 12 carbon atoms are preferred. The Rf group has a straight chain structure or a branched structure, but the straight chain structure is preferred. Further, the hydrophobic group is preferably a perfluoroalkyl group in which substantially all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. The perfluoroalkyl group is preferably a group represented by C _n F _{2n + 1} — (where n is an integer of 4 to 16), and particularly preferably when n is an integer of 6 to 12. The perfluoroalkyl group may have a linear structure or a branched structure, and a linear structure is preferred.

  The above materials are well known and described in detail in JP-A-3-178478 (Patent No. 2796575), etc., and become lyophilic when brought into contact with a liquid or solid in a heated state, and sparse when heated in air. It has the property of becoming liquid. That is, the critical surface tension can be changed by applying thermal energy (selecting the contact medium).

Furthermore, examples of the hydrophobic group include groups having a terminal structure such as —CH ₂ CH ₃ , —CH (CH ₃ ) ₂ , and —C (CH ₃ ) ₃ that do not contain a fluorine atom. Also in this case, in order to facilitate the orientation of molecular chains, a group having a long carbon chain length is preferable, and a group having 4 or more carbon atoms is more preferable. The hydrophobic group may have a linear structure or a branched structure, but a linear structure is preferred. The alkyl group may contain a halogen group, a cyano group, a phenyl group, a hydroxyl group, a carboxyl group, or a phenyl group substituted with a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an alkoxy group. Good. It is considered that the more R binding sites, the lower the surface energy (the smaller the critical surface tension) and the more lyophobic. It is inferred that, due to ultraviolet irradiation or the like, a part of the bond is broken or the orientation state changes, so that the critical surface tension increases and becomes lyophilic.

  Examples of the polymer material having a hydrophobic group in the side chain include a polymer material containing polyimide. Polyimide is excellent in electrical insulation, chemical resistance, and heat resistance, so when forming an electrode layer, etc. on the insulating wetting change layer, swelling or cracks may occur due to temperature change due to solvent or baking. Absent. Therefore, in the laminated structure 1, it is possible to form the highly reliable insulating wetting change layer 2 that is excellent in electrical insulation and is not damaged during the manufacturing process. In the case where the insulating wetting change layer 2 is composed of two or more types of materials, in consideration of heat resistance, solvent resistance and affinity, materials other than the polymer material having a hydrophobic group in the side chain are also polyimide. It is desirable to consist of.

Furthermore, the relative dielectric constant of the polyimide material is generally lower than the relative dielectric constant of SiO _{2 which} is a general insulating material, and is suitable as an interlayer insulating film. The hydrophobic group of the polyimide having a hydrophobic group in the side chain used in this embodiment can have any one of the chemical formulas shown in the following chemical formulas 1 to 5, for example.

Here, X is —CH ₂ — or —CH ₂ CH ₂ —, and A ¹ is 1,4-phenylene substituted with 1,4-cyclohexylene, 1,4-phenylene or 1 to 4 fluorines. A ² , A ³ and A ⁴ are each independently a single bond, 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene substituted with 1 to 4 fluorines, B ¹ , B ² and B ³ are each independently a single bond or —CH ₂ CH ₂ —, B ₄ is alkylene having 1 to 10 carbon atoms, and R ³ , R ⁴ , R ⁵ , R ⁶ , And R ⁷ are each independently alkyl having 1 to 10 carbon atoms, and p is an integer of 1 or more.

  In the chemical formula of Chemical Formula 2, T, U and V are each independently a benzene ring or a cyclohexane ring, and any H on these rings is alkyl having 1 to 3 carbon atoms, fluorine-substituted alkyl having 1 to 3 carbon atoms , F, Cl or CN, m and n are each independently an integer from 0 to 2, h is an integer from 0 to 5, and R is H, F, Cl, CN or Two U in the case of a monovalent organic group and m being 2 or two V in the case where n is 2 may be the same or different.

In the chemical formula of Chemical Formula 3, the linking group Z is CH ₂ , CFH, CF ₂ , CH ₂ CH ₂ or CF ₂ O, and the ring Y is 1,4-cyclohexylene or 1 to 4 Hs are F or CH 3. 1,4-phenylene which may be substituted with, A ^{1 to} A ³ are each independently a single bond, 1,4-cyclohexylene or 1 to 4 H are substituted with F or CH ³ 1,4-phenylene, and B ^{1 to} B ³ are each independently a single bond, alkylene having 1 to 4 carbon atoms, oxygen atom, oxyalkylene having 1 to 3 carbon atoms or alkylene having 1 to 3 carbon atoms. oxy, R represents H, any of the CH ₂ is 1 to 10 carbon atoms which may be substituted by CF ₂ alkyl or 1 CH ₂ is substituted are also good number 1-9 carbon in CF _2, Alkoxy or alkoxyalkyl The bonding position of the amino group to the benzene ring is arbitrary position. However, when Z is CH ₂ , all of B ^{1 to} B ³ are not simultaneously alkylene having 1 to 4 carbon atoms, Z is CH ₂ CH ₂ , and ring Y is 1, 4 When it is -phenylene, both A ¹ and A ² are not a single bond, and when Z is CF ₂ O, ring Y is not 1,4-cyclohexylene. .

Of the 4 formulas, R2 is hydrogen atom or an alkyl group having 1 to 12 carbon atoms, _{Z 1} is a CH2 group, m is 0 to 2, ring A is a benzene ring or a cyclohexane ring, 1 Is 0 or 1, each Y ₁ is independently an oxygen atom or a CH ₂ group, and each n ₁ is independently 0 or 1.

In the chemical formula of Chemical Formula 5, each Y ₂ is independently an oxygen atom or a CH ₂ group, R 3 and R 4 are independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a perfluoroalkyl group, at least one of which is carbon It is an alkyl group of several or more, or a perfluoroalkyl group, and each n ₂ is independently 0 or 1.

  Details of these materials are described in detail in JP-A No. 2002-162630, JP-A No. 2003-96034, JP-A No. 2003-267982, and the like. As for the tetracarboxylic dianhydride constituting the main chain skeleton of these hydrophobic groups, various materials such as aliphatic, alicyclic and aromatic materials can be used. Specifically, pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, and the like. In addition, materials described in detail in JP-A-11-193345, JP-A-11-193346, JP-A-11-193347, and the like can also be used.

  As described above, the polyimide containing the hydrophobic group of the chemical formula shown by Chemical Formula 1 to Chemical Formula 5 may be used alone, or may be used by mixing with other materials. However, when mixed and used, considering the heat resistance, solvent resistance, and affinity, the material to be mixed is also preferably polyimide. Moreover, the polyimide containing the hydrophobic group which is not shown by the chemical formula shown by Chemical formula 1-Chemical formula 5 can also be used.

  The thickness of the insulating wetting change layer 2 in this embodiment is preferably 30 nm to 3 μm, and more preferably 50 nm to 1 μm. If it is thinner than this, properties (insulating properties, gas barrier properties, moisture resistance, etc.) as a bulk body are impaired, and if it is thicker than this, the surface shape deteriorates, which is not preferable.

  By the way, there is ultraviolet irradiation as a method of applying energy for changing the critical surface tension. When energy is applied by such ultraviolet irradiation, a fine pattern can be easily formed. For example, as shown in FIG. 14A, the insulating wetting change layer 2 is laminated on the electrode (first conductive material) 7 of the substrate 6, and the exposure mask 16 is formed on the surface of the insulating wetting change layer 2. And an ultraviolet ray 17 is irradiated through the exposure mask 16. Then, as shown in FIG. 14B, a pattern composed of the critical surface tension of the low surface energy portion 4 and the high surface energy portion 3 is formed in the insulating wetting change layer 2. It is desirable that the ultraviolet rays include light having a relatively short wavelength of 100 nm to 300 nm.

  A process of forming the insulating wetting change layer 2 on at least the first conductive material layer 7 on the laminated structure 1 described above and a low critical surface tension with a low critical surface tension by applying energy to a part of this material. A step of forming a pattern having a different critical surface tension comprising a surface energy portion 4 and a high surface energy portion 3 having a high critical surface tension; and a liquid containing a second conductive material is applied to the high surface energy on the pattern. When the interlayer insulating film (2) is formed between the electrode (4, 3) formed in the two layers and the electrode 7 by being applied to the portion 3, the manufacturing process is simple and the structure is fine. An electronic device 20 can be provided. As a method for applying a liquid containing a conductive material in this embodiment, a known printing method such as a lithographic printing method, a relief printing method, an intaglio printing method, and a stencil printing method can be applied.

  By using at least one of the wettability changing material and the manufacturing method described in the laminated structure 1 and the manufacturing method thereof as the insulating wetness changing layer 2 described above, High value-added functions such as high resistance, low dielectric constant, high dielectric constant, process resistance, and simple fine patterning can be provided.

  In the laminated structure 1 and the electronic element 20 described above, when a part of the insulating wetting change layer 2 is removed and the first and second conductive material layers are connected to each other by the removal portion 19, FIG. Since such multilayer wiring and wiring connection between layers are possible, the electronic element 20 can be highly integrated. For example, as shown in FIG. 15, in the laminated structure 1 and the electronic element 20, after forming the insulating wetting change layer 2, a desired portion is ablated and removed by a laser or the like, and the second conductive of the removing unit 19 is removed. It can be obtained by applying energy only to the conductive material layer film forming portion to obtain high surface energy, and forming the second conductive material layer 5 there.

  As a method for applying one of the liquids containing the first and second conductive materials 7 and 5 to the surface of the material on which the wettability pattern is formed, a known spin coating method, dipping method, blade coating method, spray Any one of the coating methods may be used. By using such a method, the element manufacturing time can be significantly shortened and a printing apparatus is not required, so that the manufacturing cost can be greatly reduced.

  As a method of applying one of the liquids containing the first and second conductive materials 7 and 5 to the surface of the material on which the wettability pattern is formed, a known ink jet method may be used. In this case, the conductive layer can be formed only on the high surface energy part. For example, as shown in FIG. 16B, the substrate 6, the first conductive material layer 7, and the insulating wetting change layer 2 are stacked in this order, and a plurality of electrodes 5 are formed on the surface of the insulating wetting change layer 2. When the electrode wiring is miniaturized, as shown in FIG. 16C, the distance between the electrodes 3 decreases, and this may cause a short circuit when applying the conductive material. In this embodiment, as shown in FIG. 16 (a), it is possible to apply a conductive material only to the high surface energy portion 3, so that a highly reliable manufacturing process can be performed in microfabrication without such a situation. It can be provided.

  The electronic device manufactured by the manufacturing method described above can be applied to the liquid crystal display device 30 shown in FIG. In this case, the manufacturing process can be reduced as compared with the conventional case, and an inexpensive display element can be provided. FIG. 17 shows a wiring diagram of the liquid crystal display element. In the figure, a voltage is applied from the gradation signal line 31 according to the gradation of an active cell 35 as a pixel to which a capacitor 33 and a liquid crystal cell 34 are connected. Further, an ON / OFF signal voltage is sequentially applied from the scanning line 32 line by line, and after the scanning of one screen is completed, the scanning of the next screen is started. In the case of video support, this interval is preferably 50 Hz or more (1/50 sec. Or less). The capacitor 33 has a function of charging the voltage of the gradation signal for the time from the transition from one screen to the next screen.

  Thus, the insulating wetting change layer 2 is used not only as an interlayer insulating film but also as a capacitor 33 in the case of a liquid crystal display element. In this case, it is preferable to use a low dielectric constant material for the interlayer insulating film and a high dielectric constant material for the capacitor for the insulating wetting change layer.

The use form of the electronic element manufactured by the above-described manufacturing method can be applied to an arithmetic element. In this case, the manufacturing process can be reduced as compared with the prior art, and an inexpensive arithmetic element can be provided. For example, when it is applied as shown in FIGS. 20 and 21, it is preferable to use a low dielectric constant material for the interlayer insulating film in order to improve the operating frequency.
When an electronic element or an arithmetic element is manufactured as described above, the element can be manufactured by a very inexpensive manufacturing process, and thus the manufacturing cost can be greatly reduced.

FIG. 18 shows the process of the present example. First, as shown in FIG. 18A, the insulating wettability changing layer 2 is formed on the glass substrate 50 to be a structure represented by Chemical Formulas 6 and 7 after firing. A mixed solution in which the precursor was dissolved was applied by spin coating and baked at 200 ° C. The volume resistivity of this material was 5 × 10 ¹³ Ω · cm.

As shown in FIG. 18B, a mask 52 having a pattern with an opening width of 40 μm and a space between openings of 5 μm was pressure-bonded to change in wettability, and ultraviolet rays 53 were irradiated at 9 J / cm ² . The critical surface tension was about 24 mN / m for the unirradiated part and about 45 mN / m for the part irradiated with ultraviolet rays.

Next, as shown in FIG. 18C, an aqueous solution 54 of PEDOT / PPS, which is a conductive polymer, was supplied to the high surface energy portion 55 on the insulating wetting change layer 51 using an ink jet method. As shown in FIG. 18D, after baking at 200 ° C. to form the electrode layer 56, the insulating wetting change layer 51 was formed in the same manner as in the process of FIG. Next, as shown in FIG. 18 (e), the structure shown in FIG. 18 (b) and FIG. 18 (c) is used, an electrode layer 56 is formed thereon, and electrodes are stacked via an insulating material. Produced.
[Comparative Example 1]

As shown in FIG.
・ Sequential deposition of Cr and Au on the glass substrate ・ Pattern the electrode by the process A described in the section of the background art ・ Sputter deposition of SiO2 on the patterned electrode (sputtering film)
-Cr and Au were sequentially deposited on the sputtered film, and the electrode was patterned again by the process A.-A laminated structure having a function corresponding to Fig. 18 (e) was manufactured by the above process.

  In Example 1, the manufacturing process can be greatly simplified as compared with the case where SiO2 as shown in Comparative Example 1 is used as an insulating material and electrode patterning is performed by a photolithography process.

It is a cross-sectional schematic diagram which shows the example of a fundamental structure of the laminated structure which is one embodiment of this invention. It is a schematic diagram showing a state when a droplet is in an equilibrium state at a contact angle θ on the solid surface for explaining the wettability of the liquid with respect to the solid surface. Surface tension showing the result of performing Zisman plots between the unirradiated part and the irradiated part when the mixture of polyimides represented by the chemical formula of chemical formula A and chemical formula of chemical formula 7 is used for the wettability changing layer after firing- It is a contact angle characteristic view. It is a cross-sectional schematic diagram which shows one form of an insulating wetting change layer. It is a cross-sectional schematic diagram which shows the form of the insulating wetting change layer with distribution in a layer film direction. It is a cross-sectional schematic diagram which shows another form of the insulating wetting change layer with distribution in a layer film direction. It is a cross-sectional schematic diagram which shows another form of the insulating wetting change layer with distribution in a layer film direction. It is a cross-sectional schematic diagram which shows another form of the insulating wetting change layer with distribution in a layer film direction. It is a cross-sectional schematic diagram which shows another form of the insulating wetting change layer with distribution in a layer film direction. It is a cross-sectional schematic diagram which shows the form of the insulating wetting change layer in which a 2nd material has a higher electrical insulation than a 1st material. It is a cross-sectional schematic diagram which shows the form of the insulating wetting change layer whose 2nd material has a dielectric constant lower than a 1st material. It is a cross-sectional schematic diagram which shows the form of the insulating wetting change layer whose 2nd material has a dielectric constant higher than a 1st material. It is a conceptual diagram of the polymeric material which contains a hydrophobic group in the side chain used for an insulating wetting change layer. It is a schematic cross section which shows the form of the process of forming a fine pattern by ultraviolet irradiation, and the form of an insulating wetting change layer. It is a schematic cross section which shows the structure of the laminated structure which removed a part of insulating wet change layer, and connected two electroconductive material layers. It is a schematic cross-sectional view of an insulating wetting change layer showing a demilit because of the merit when an electrode is configured by applying a conductive material to a material surface on which a wettability pattern is formed. It is a wiring diagram of a liquid crystal display element which is one form of a display element using a multilayer structure. It is a figure which shows one form of the manufacturing process of a laminated structure. It is a schematic cross section which shows one form of the conventional manufacturing process and the laminated structure manufactured by the curvature. It is an enlarged view showing an embodiment of an arithmetic circuit. It is an enlarged view showing one form of arithmetic elements integrated / connected via an interlayer insulating film. It is an enlarged view which shows one form of a display apparatus.

Explanation of symbols

1 Laminated structure 2, 51 Insulating material layer (insulating wetting change layer)
3, 55 High surface energy part 4 Low surface energy part 5 Second conductive material (electrode)
7 First conductive material 13 First material 14, 24, 34, 44 Second material 17, 53 Ultraviolet ray 19 Removal part 20, 33 Electronic element 30, 86 Display element 60, 70 Arithmetic element C Film thickness direction

Claims (22)

In a laminated structure in which an insulating material layer is laminated on at least a first conductive material, and a second conductive material is laminated thereon,
The insulating material layer is an insulating wetting change layer having an insulating function and a function of changing the critical surface tension by applying energy, and the second conductive material is a high surface energy portion of the insulating wetting change layer. It is formed in the site | part of the laminated structure characterized by the above-mentioned. The laminated structure according to claim 1, wherein
The laminated structure characterized by the solvent used for film-forming of the said insulation wet change layer containing the organic solvent which can be melt | dissolved with water and arbitrary ratios. The laminated structure according to claim 1 or 2,
The insulating wetting change layer has a low surface energy portion and a high surface energy portion formed by energy irradiation, and a difference between the critical surface tension of the low surface energy portion and the critical surface tension of the high surface energy portion is 10 mN / m. A laminated structure characterized by the above. In the laminated structure according to claim 1, 2, or 3,
The insulating wetting change layer is made of two or more kinds of materials, and is a laminated structure. The laminated structure according to claim 4, wherein
The insulating wetting change layer has at least a first material whose critical surface tension is largely changed by relatively applying energy, and a second material having a higher electrical insulation than the first material. A laminated structure characterized by that. The laminated structure according to claim 4, wherein
The insulating wetting change layer has at least a first material whose critical surface tension is largely changed by application of energy, and a second material having a low dielectric constant compared to the first material. A laminated structure characterized by the above. The laminated structure according to claim 4, wherein
The insulating wetting change layer has at least a first material whose critical surface tension is largely changed by application of energy, and a second material having a higher dielectric constant than the first material. A laminated structure characterized by the above. In the laminated structure according to any one of claims 1 to 7,
A laminated structure characterized in that a material whose critical surface tension greatly changes by application of energy is a polymer material containing a hydrophobic group in a side chain. The laminated structure according to claim 8, wherein
The laminated structure, wherein the polymer material having a hydrophobic group in the side chain is made of a polymer material containing polyimide. In the laminated structure according to any one of claims 1 to 9,
A laminated structure characterized in that application of energy for changing the critical surface tension is ultraviolet irradiation. In the laminated structure according to any one of claims 1 to 9,
A part of the insulating wetting change layer is removed, and the first and second conductive material layers are connected to each other at the removal portion. Forming an insulating wetting change layer on at least the first conductive material layer;
Forming a pattern with different critical surface tensions comprising a low surface energy part having a low critical surface tension and a high surface energy part having a high critical surface tension by applying energy to a portion of the insulating wetting change layer; and ,
And a step of forming an interlayer insulating film between electrodes formed in two layers by applying a liquid containing a second conductive material to the high surface energy portion on the pattern. Manufacturing method of structure. In the manufacturing method of the laminated structure of Claim 12,
A method for producing a laminated structure, wherein the application of energy for changing the critical surface tension is ultraviolet irradiation.   An electronic device comprising the laminated structure according to claim 1 as a constituent element.   An electronic device comprising a laminated structure produced by the method for producing a laminated structure according to claim 12 or 13 as a constituent element. The electronic device according to claim 13 or 14,
An electronic element, wherein a part of the insulating wetting change layer is removed, and the first and second conductive material layers are connected to each other by the removal portion. A method of manufacturing an electronic device according to claim 14, 15 or 16,
The method of applying at least one of the liquids containing the first and second conductive materials to the surface of the material on which the wettability pattern is formed is any one of a spin coating method, a dipping method, a blade coating method, and a spray coating method. A method for manufacturing an electronic device, characterized in that: A method of manufacturing an electronic device according to claim 14, 15 or 16,
A method for producing an electronic device, wherein the method of applying at least one of the liquids containing the first and second conductive materials to the surface of the material on which the wettability pattern is formed is an ink jet method.   A display device comprising the electronic device according to claim 14, 15 or 16.   An arithmetic element using the electronic element according to claim 14, 15 or 16.   A display element manufacturing method, wherein the display element according to claim 19 is manufactured using the electronic element manufacturing method according to claim 17 or 18.   An arithmetic element manufacturing method, wherein the arithmetic element according to claim 20 is manufactured using the electronic element manufacturing method according to claim 17 or 18.

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