JP5287015B2 - Patterning method, organic electric element, organic electroluminescent element, and organic semiconductor transistor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a patterning method for suppressing residues at a pattern formation process from remaining in a formed recessed part or a hole in the formation of a pattern on a pattern formed layer. <P>SOLUTION: The organic semiconductor transistor element 40 includes an insulating layer 47 formed by uniformly coating an insulating material for forming a barrier wall 49 on a substrate 42 with a source electrode 44 and a drain electrode 45 formed thereon as shown in Fig.8 in a manufacturing process. A mold 60 which has a projection 60A corresponding to a pattern to be formed and is coated with a solution 62 for dissolving the insulating layer on the projection part 60A is brought into contact with the insulating layer 47. Thereby, the insulating layer 47 is dissolved and the hole part 49A corresponding to the projection part 60A is formed, and then the mold 60 is separated from the substrate 42 to pattern the hole 49A. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a patterning method, an organic electric element, an organic electroluminescent element, and an organic semiconductor transistor.

  2. Description of the Related Art Conventionally, techniques for forming patterns on various substrates are known. As a method for forming such a pattern (patterning method), photolithography is generally used, and a latent image is formed through a photomask on a photosensitive material called uniformly applied resist, A desired pattern is obtained by removing unnecessary portions with an etching solution (for example, Patent Documents 1 to 3). For example, a functional material such as an organic compound is poured into a recess or a hole in a partition wall provided by this pattern formation, so that a desired organic electric element or the like is produced.

As another patterning method, a method of forming a dissolution hole by an ink jet method is also known (for example, Patent Document 4). As an ink jet method, a dissolution hole is formed by discharging a solution for dissolving the insulating layer onto the insulating layer, or patterning the dissolution hole by discharging a solution containing a functional material onto the insulating layer. However, a method of filling the melting hole with a functional material is used. By using such an ink jet method, it is not necessary to align the photomask, it is not necessary to prepare a photomask according to the pattern, and it is easy to apply to a large pattern formation target.
JP-A-5-335441 Japanese Patent Laid-Open No. 10-12377 JP-A-11-87063 JP 2006-253632 A

  This invention makes it a subject to achieve the following objectives. That is, the present invention is to provide a patterning method in which, in the pattern formation on the pattern formation target layer, the residue in the pattern formation step is suppressed from remaining in the formed recess or hole, as compared with the inkjet method. .

The invention according to claim 1 is a coating step of applying a solution for dissolving the pattern formation target layer to the convex portion of the mold having a convex portion corresponding to the pattern to be formed; and the mold is applied to the pattern formation target layer. A contact step of bringing the mold into contact with a side of the convex portion to which the dissolution liquid is applied, and the pattern formation target in which a concave portion or a hole portion corresponding to the convex portion is formed by dissolution with the dissolution liquid. from the layer, have a, a separation step of separating the mold, is greater than the thickness of the thickness of the convex portion is the patterned target layer, a patterning method.

The invention according to claim 2 is the patterning method according to claim 1 , wherein, in the application step, the solution is applied over the entire surface of the mold on the side where the convex portions are formed. is there.
The invention according to claim 3 is characterized in that, in the application step, the solution is applied after the region of the mold to which the solution is applied is made lyophilic with respect to the solution. A patterning method according to claim 1 or 2 .
The invention according to claim 4, in the contacting step, after contacting the mold to the patterned target layer, in any one of claims 1 to 3, characterized in that to heat and dry The patterning method described.

The invention according to claim 5 is the patterning method according to any one of claims 1 to 4 , wherein the mold is made of metal.
The invention according to claim 6 is the patterning method according to any one of claims 1 to 4 , wherein the mold has elasticity.
The invention according to claim 7 is the patterning method according to any one of claims 1 to 6 , wherein the solution contains a solid component.
The invention according to claim 8 is the patterning method according to claim 7 , wherein the solid component is a material constituting the pattern formation target layer.

The invention according to claim 9 is a partition member formed between a pair of electrodes, a functional part formed between the pair of electrodes and composed of one or a plurality of organic compound layers, and dividing the functional part into a plurality of regions. And at least one of the pair of electrodes includes one or a plurality of electrode groups, and the partition member is formed with a hole by the patterning method according to any one of claims 1 to 8. and a pattern formation target layer, wherein the functional unit, the one or more the holes formed in the pattern forming object layer by a patterning method according to any one of claims 1 to 8 the organic compound layer is an organic electronic device which is formed by being filled in.

The invention according to claim 10 is a partition member formed between a pair of electrodes, a light emitting portion formed between the pair of electrodes and composed of one or more organic compound layers, and dividing the light emitting portion into a plurality of regions. And at least one of the pair of electrodes includes one or a plurality of electrode groups, and the partition member is formed with a hole by the patterning method according to any one of claims 1 to 8. and a pattern formation target layer, the light emitting unit, the one or more the holes formed in the pattern forming object layer by a patterning method according to any one of claims 1 to 8 It is an organic electroluminescent element formed by being filled with the organic compound layer.

According to an eleventh aspect of the present invention, there is provided a functional unit including a source electrode, a drain electrode, an organic semiconductor layer provided to be conductive with the source electrode and the drain electrode, and insulated from the functional unit. A plurality of organic semiconductor transistor elements including a gate electrode to which an electric field is applied are arranged, and a partition member that insulates between the organic semiconductor transistor elements is provided, and the partition member is any one of claims 1 to 8. a pattern formation target layer formed of the hole by the patterning method according to item 1, wherein the functional unit is a patterned target layer by the patterning method according to any one of claims 1 to 8 It is an organic semiconductor transistor formed by filling the organic semiconductor layer in the formed hole.

According to the first aspect of the present invention, compared to the ink jet method, in pattern formation on the pattern formation target layer, it is possible to suppress the residue in the pattern formation process from remaining in the formed recess or hole. Play.
Moreover, according to the invention which concerns on Claim 1, there exists an effect that a through-hole is easily formed in a pattern formation object layer by simple structure.

According to the invention of claim 2 , in addition to the effect of the invention of claim 1, there is an effect that the solution can be easily applied to the mold with a simple configuration.
According to the invention of claim 3 , in addition to the effect of the invention of claim 1 or claim 2 , the effect that the solution is uniformly held in the region where the solution of the mold is applied is provided. Play.

According to the invention of claim 4 , in addition to the effects of the inventions of claims 1 to 3 , in the formed recesses or holes in the pattern formation target layer after the mold is peeled off by the peeling step There is an effect that the dissolution material and the formation material of the pattern formation target layer are prevented from entering the recesses or the hole portions to be blocked.

According to the invention according to claim 5 , in addition to the effects produced by the invention according to claims 1 to 4 , a mold corresponding to the flexibility of the pattern formation target layer is selected, and preferably on the convex part of the mold There is an effect that a corresponding recess or hole is formed.

According to the invention according to claim 6 , in addition to the effects produced by the invention according to claims 1 to 4 , a mold corresponding to the flexibility of the pattern formation target layer is selected, and preferably on the convex part of the mold There is an effect that a corresponding recess or hole is formed.

According to the invention of claim 7 , in addition to the effects of the inventions of claims 1 to 6 , the viscosity of the solution is easily adjusted, and a residue is formed in the formed hole or recess. There is an effect that the remaining is further suppressed.

According to the eighth aspect of the invention, in addition to the effect of the seventh aspect of the invention, there is an effect that it is possible to prevent a decrease in insulation and weather resistance due to the solid component.

According to the ninth aspect of the present invention, there is an effect that the organic electric element can have a long life as compared with the case where patterning is performed by the ink jet method.

According to the invention concerning Claim 10 , compared with the case where it patterns by the inkjet method, there exists an effect that an organic electroluminescent element can be made long life.

According to the eleventh aspect of the present invention, there is an effect that the drivability of the organic semiconductor transistor is improved as compared with the case where patterning is performed by the ink jet method.

Hereinafter, one embodiment of the patterning method of the present invention will be described.
In the patterning method of the present embodiment, a substrate on which a pattern formation target layer to be a pattern formation target is formed is prepared. And it has the convex part according to the pattern of the formation object, and by making the pattern application object layer melt | dissolve by making the casting_mold | template with the solution which melt | dissolves the pattern formation object layer at least to this convex part, A concave portion or a hole portion corresponding to the convex portion is patterned on the pattern formation target layer. Thereafter, the pattern is peeled from the substrate to form a pattern formation target layer in which concave portions or hole portions corresponding to the convex portions of the mold are patterned.

  By using this patterning method, the present inventors are able to suppress residues remaining in the manufacturing process from remaining in the recesses or holes patterned in the pattern formation target layer, and to reduce the recesses in a simple process. Alternatively, it has been found that a hole is formed and a partition formed by a recess or a hole is formed. The details will be described below.

(First embodiment)
In the present embodiment, a case where the patterning method is applied to manufacturing an organic EL (Electroluminescent) element will be described.

  As shown in FIG. 1, the organic EL element 10 formed in this embodiment includes a substrate 12, an electrode 14, a functional layer 20, and an electrode 16 that are sequentially stacked and provided adjacent to each other in the surface direction of the substrate 12. Further, a partition wall 18 is provided that insulates the plurality of functional layers 20 and insulates between the electrode 16 and the electrode 14.

The substrate 12 is preferably transparent (visible light transmittance is 50% or more, the same applies hereinafter) to extract emitted light. For example, a glass substrate, a plastic substrate, a quartz substrate, a PET substrate, a PEN substrate, or the like is used. However, it is not limited to these.
In particular, the organic EL element 10 of the present embodiment is used in an electronic circuit used in an electronic device (hereinafter, referred to as “flexible electronic device”) that is required to be flexible, such as electronic paper, digital paper, or portable electronic equipment. When using this, it is desirable to use a flexible substrate 12 as the substrate 12. In particular, by using the substrate 12 having a flexural modulus of 1000 MPa or more, more preferably 5000 MPa or more as the substrate 12, the substrate 12 can be applied to a flexible display element driving circuit or electronic circuit.

  The electrode 14 is preferably transparent so as to extract emitted light as in the case of the substrate 12, and preferably has a high work function for injecting holes. Indium tin oxide (ITO), tin oxide (NESA), indium oxide In addition, an oxide film such as zinc oxide and gold, platinum, palladium or the like deposited or sputtered are used. Further, a material selected from these materials is configured by mixing and laminating one kind or plural kinds as required.

As shown in the manufacturing process described later, the electrode 16 is made of a metal that can be vacuum-deposited and has a low work function in order to inject electrons. Particularly preferably, magnesium, aluminum, gold, silver, copper, Chromium, tantalum, indium, palladium, lithium, calcium, and alloys thereof are used. Alternatively, a metal oxide such as magnesium oxide, aluminum oxide, indium tin oxide (ITO), tin oxide (NESA), indium oxide, zinc oxide, or indium zinc oxide may be used. Further, a material selected from these materials is configured by mixing and laminating one kind or plural kinds as required.

  Note that at least one of the electrode 14 and the electrode 16 is preferably transparent or translucent (transmittance to visible light is 30% to 50%, and the same applies hereinafter).

The partition wall 18 is made of an insulating material (10 ¹² Ωcm or more in volume resistance, hereinafter referred to as an insulating material) (hereinafter referred to as an insulating material), and is used on the substrate 12 in the manufacturing process of the organic EL element 10 to be described later. It is important to have suitable film forming characteristics when formed as an insulating layer. In addition, this insulating material is easily dissolved in a solution used in the manufacturing process of the organic EL element 10 to be described later (the number of grams of the insulating material dissolved in 100 g of the solution is 0.1 g or more and below) In addition, the material constituting the functional layer 20 is hardly soluble (the number of grams of the insulating material dissolved in 100 g of the solution is 0.01 g or less, and the same applies hereinafter). It is necessary to satisfy the condition.

  As such an insulating material, in the combination of the functional layer 20 used in the organic EL element 10 of the present embodiment and a solution to be described later, an acrylic resin such as polyimide resin or polymethyl methacrylate (PMMA) is used. And a cycloolefin polymer are preferably used, but may be appropriately selected according to the material used for the functional layer 20 constituting the organic EL element 10 and the material used as the solution, and is limited to such a material. Absent.

  The functional layer 20 is composed of an organic compound layer composed of two or more layers sandwiched between a pair of electrodes (between the electrode 14 and the electrode 16). Here, in this organic compound layer, at least one layer is a light emitting layer, and the other layer is composed of a charge transport layer such as one or both of a hole transport layer and an electron transport layer.

For example, in the organic EL element 10 shown in FIG. 2, the functional layer 20 is configured by sequentially stacking a hole transport layer 20C, a light emitting layer 20B, and an electron transport layer 20A. Further, for example, in the organic EL element 10 shown in FIG. 3, the functional layer 20 is configured by laminating a buffer layer 20 </ b> C, a hole transport layer 20 </ b> D, a light emitting layer 20 </ b> B, and an electron transport layer 20 </ b> A in order. Yes.
Moreover, in the organic EL element 10 shown in FIG. 4, the functional layer 20 is comprised from 20 C of buffer layers, and the light emitting layer 20E with a carrier transport ability. In the organic EL element 10 shown in FIG. 5, the functional layer 20 is configured by sequentially stacking a buffer layer 20C, a hole transport layer 20D, and a light emitting layer 20B.

  As a charge transport material (hole transport material, electron transport material) used for charge transport of each layer constituting the functional layer 20 (organic compound layer), for example, a polymer charge transport material is used. As such a polymer charge transport material, for example, a material containing at least one selected from the structures represented by the following general formulas (I-1) to (I-6) in the repeating unit structure is preferable. However, the present invention is not limited to this.

  In the above general formulas (I-1) to (I-6), n represents an integer of 1 to 5000.

  In the organic EL device as shown in FIG. 2, a compound that exhibits a high fluorescence quantum yield in the solid state is used as the light emitting material for the light emitting layer 20B. When the light emitting material is a low molecular weight organic material, it is a condition that a thin film can be satisfactorily formed by applying and drying a vacuum deposition method or a solution or dispersion containing a low molecular weight and a binder resin. Further, when the light emitting material is a polymer, it is a condition that a thin film can be satisfactorily formed by applying and drying a solution or dispersion containing itself.

  When the light-emitting material is a low-molecular-weight organic material, preferably a chelate-type organometallic complex, a polynuclear or condensed aromatic ring compound, a perylene derivative, a coumarin derivative, a styrylarylene derivative, a silole derivative, an oxazole derivative, an oxathiazole derivative, an oxadiazole derivative When the light emitting material is an organic polymer, a polyparaphenylene derivative, a polyparaphenylene vinylene derivative, a polythiophene derivative, a polyacetylene derivative, a polyfluorene derivative, or the like is preferably used. As preferred specific examples, the following compounds (II-1) to (II-17) are used, but are not limited thereto.

  Further, for the purpose of improving the durability of the organic EL element 10 or improving the light emission efficiency, the light emitting material may be doped with a dye compound different from the light emitting material as a guest material. When the light emitting layer 4 is formed by vacuum deposition, doping is performed by co-evaporation, and when the light emitting layer 4 is formed by applying and drying a solution or dispersion, doping is performed by mixing in the solution or dispersion. .

  The doping ratio of the dye compound in the light emitting layer 20B is about 0.001% by mass to 40% by mass, preferably about 0.001% by mass to 10% by mass. As the coloring compound used for such doping, an organic compound that has good compatibility with the light emitting material and does not hinder the formation of a good thin film of the light emitting layer 20B is used, and preferably a DCM derivative, a quinacridone derivative, rubrene. Derivatives, porphyrins and the like are used. Preferable specific examples of such compounds include the following compounds (III-1) to (III-5), but are not limited thereto.

  In addition, as a light emitting material, an organic EL element can be used in the case where a material that does not become a good thin film or that does not show a clear electron transport property can be applied by vacuum deposition, solution or dispersion, or drying. For the purpose of improving the durability or the light emission efficiency, an electron transport layer 20A may be inserted between the light emitting layer 20B and the electrode 16 as in the organic EL element 10 shown in FIG.

  As an electron transport material used for such an electron transport layer, an organic compound capable of forming a good thin film by a vacuum deposition method is used, and preferably an oxadiazole derivative, a nitro-substituted fluorenone derivative, a diphenoquinone derivative, a thiopyran. Dioxide derivatives, fluorenylidenemethane derivatives and the like are used. Preferred specific examples include, but are not limited to, the following compounds (VIII-1) to (VIII-3) and (IX).

The organic EL element 10 of the present embodiment configured as described above applies a DC voltage of 1 to 200 mA / cm ² at a current density of, for example, 4 to 20 V between a pair of electrodes (between the electrode 16 and the electrode 14). To emit light.

<Method for producing organic EL element>
Next, the manufacturing method of the organic EL element 10 of this Embodiment is demonstrated.
The organic EL element 10 of this Embodiment is suitably manufactured using the patterning method demonstrated below.

  As described above, in the organic EL element 10 of the present embodiment, in the manufacturing process of the organic EL element 10, the insulating material constituting the partition wall 18 is uniformly formed on the substrate 12 on which the electrodes 14 are formed. The insulating layer is formed by coating, and the insulating layer is provided with a convex portion 30A corresponding to the pattern to be formed, and the convex portion 30A applied with a solution 32 for dissolving the insulating layer is brought into contact with the convex portion 30A. Then, the hole is patterned by peeling the mold 30 from the substrate 12 after dissolving the insulating layer to form the hole 18A corresponding to the convex portion 30A. As a result, a hole for filling the functional layer 20 is formed in the insulating layer. And after forming the functional layer 20 by filling the material which comprises the functional layer 20 in this formed hole part, it produces by providing the electrode 16. FIG. Details will be described below.

As shown in FIG. 6A, first, a substrate 12 provided with an electrode 14 is prepared. Then, as shown in FIG. 6B, an insulating layer 17 that finally functions as the partition wall 18 is formed by uniformly applying the insulating material for forming the partition wall 18 on the substrate 12. Form.
As described above, as the insulating material, a material having excellent insulating properties and satisfying a good film forming condition is used, and it is difficult for a material that forms a functional layer 20 to be dissolved in a solution to be described later. Any material may be used as long as it satisfies the property of being dissolved.

  Further, the above “good film forming conditions” mean that the in-plane film thickness distribution is the center when the insulating layer 17 is formed by applying the insulating material onto the substrate 12 on which the electrode 14 is formed with the insulating material. The condition of ± 20% or less from the value is shown.

  As a method of applying the insulating material onto the substrate 12, methods such as spin coating, dipping, and casting may be used, and various methods such as ink jet, printing, and barcode may be used. Not limited.

Next, a mold 30 having a convex portion 30A corresponding to a pattern (in this embodiment, a hole for forming the functional layer 20) formed on the insulating layer 17 is prepared.
As the mold 30, when a flexible substrate 12 is used as the substrate 12, it is preferable to use a mold that is as flexible as the substrate 12 in terms of adhesion between the substrate and the mold. .

Next, a solution is applied to the convex portion 30A of the mold 30 (FIG. 6C). In the present embodiment, it is assumed that the thickness of the convex portion 30 </ b> A is adjusted to be larger than the thickness of the insulating layer 17 formed on the substrate 12.
By adjusting the thickness of the convex portion 30A to be larger than the thickness of the insulating layer 17, in a process described later, the concave portion formed in the insulating layer 17 according to the convex portion 30A causes the insulating layer 17 to move in the thickness direction. It is formed as a through hole that penetrates.

  In the present embodiment, a through hole penetrating the insulating layer 17 is provided by the mold 30 on which the convex portion 30A is formed, and the functional layer 20 is filled with a functional layer 20 to be described later, so that the functional layer 20 becomes the electrode 14. Since the thickness of the convex portion 30A is adjusted in advance to be larger than the thickness of the insulating layer 17, for example, when it is desired to simply provide a non-penetrating concave portion in the insulating layer 17, It goes without saying that the thickness of the recess 30 </ b> A may be less than the thickness of the insulating layer 17.

  Then, a solution for dissolving the insulating layer 17 is applied to the convex portions 30 </ b> A of the mold 30. As a method for applying the solution only to the convex portion 30A, a method of dipping only the convex portion in the solution (dip method) or the like is used.

When the mold 30 is brought into contact with the insulating layer 17 in a process to be described later, the solution is applied to the region where the solution on the mold 30 is applied (the pattern is to be provided with a recess on the insulating layer 17). Application may be made so as to be in contact with a region to be formed).
For this reason, when a pattern corresponding to the convex portion 30A of the mold 30 is formed on the insulating layer 17, the solution is applied only to a region to be patterned when the mold 30 is brought into contact with the insulating layer 17. That's fine.

  The application amount of the dissolving liquid may be an amount in which the area where the dissolving liquid is applied on the mold 30 can dissolve the insulating layer 17 in the contact area when the mold 30 is in contact with the insulating layer 17.

  In the present embodiment, the case where the solution is applied only to the convex portion 30A will be described. However, the thickness of the convex portion 30A of the mold 30 is larger than the thickness of the insulating layer 17 as in the present embodiment. In the case where the mold 30 is adjusted, the region to be contacted when the mold 30 is brought into contact with the insulating layer 17 is only the convex portion 30A. Therefore, the solution is applied to the region other than the convex portion 30A. Also good. That is, even if the region to be melted is only the region where the convex portion 30A is in contact, when the mold 30 is brought into contact with the insulating layer 17 from the side where the convex portion 30A is provided in the process described later, the convex portion Since the portion 30A hits the electrode 14 on the substrate 12 via the insulating layer 17, the solution may be applied to the region other than the convex portion 30A of the mold 30. In this way, the solution can be easily applied by a simple process.

  As this solution, a material that forms the insulating layer 17 is dissolved, and a material that hardly dissolves may be used as the material that forms the electrode 14 and the substrate 12, and is determined according to the material that forms the insulating layer 17. It is done. Examples of the solution include isopropyl alcohol, ethylene glycol, xylene, trimethylbenzene, monochlorobenzene, orthodichlorobenzene and the like, but are not limited to these as long as the above characteristics are satisfied.

In the solution, various solid components may be dispersed or contained in order to adjust the viscosity for suppressing dripping from the mold 30. The viscosity of the solution is preferably 10 mPa · s or more and 1000 mPa · s or less, and more preferably 20 mPa · s or more and 200 mPa · s or less, from the viewpoint of suppressing dripping.
The solid component may be any material as long as it is used for viscosity adjustment and does not affect the electrical characteristics of the peripheral portion. Preferably, the insulation and weather resistance by mixing different materials are used. For the purpose of preventing the deterioration of the property, it is preferable that the same material as the material constituting the insulating layer 17 to be dissolved is included. By including the material constituting the insulating layer 17 as a solid component, even if a part of the solution remains in the hole or recess formed in the insulating layer 17, it is the same substance and therefore has chemical properties. Does not change, and the deterioration of the insulation and weather resistance due to the solid component is prevented, so that the functional degradation as an element is suppressed.

  In addition, it is preferable to apply | coat the solution 32 after performing a lyophilic process to the area | region (projection part 30A in this Embodiment) which becomes the object which applies the solution 32 of this casting_mold | template 30. FIG. By applying the dissolution liquid 32 after the surface of the mold 30 is made lyophilic, the dissolution liquid 32 causes dripping from the mold 30 or the thickness of the dissolution liquid 32 applied to the mold 30 becomes uneven. Things are suppressed.

Examples of the lyophilic treatment method include a line with an organic solvent, UV ozone treatment, plasma irradiation treatment, O ₂ ashing, ultraviolet irradiation, laser irradiation, coupling agent coating, strong acid / strong alkali treatment, graft polymerization and the like. Not limited to these.

  Next, the mold 30 having the solution 32 applied to at least the convex portion 30A is brought into contact with the substrate 12 so that the side on which the convex portion 30A is formed is in contact with the insulating layer 17 (FIG. 6D and FIG. 6). E) Contact process).

  In this contact step, the region in contact with the solution applied to the convex portion 30A in the entire region of the insulating layer 17 is brought into contact with the region where the convex portion 30A of the mold 30 is applied. Dissolved. For this reason, when the mold 30 is peeled from the substrate 12, the insulating layer 17 is formed with holes 18A corresponding to the convex portions 30A, and as a result, the holes 18A formed in the insulating layer 17 are insulated. A partition wall 18 made of a material is formed (see FIG. 6F).

  In this contact step, heat treatment is performed with the mold 30 in contact with the substrate 12 in order to dissolve the insulating layer 17 efficiently and effectively to form the hole 18A corresponding to the convex portion 30A. It is preferable to dry the solution by carrying out the process. In this contact step before peeling the mold 30 from the substrate 12, heat treatment is performed and the solution is dried, so that an undried solution remains at the interface with the insulation layer 17, thereby forming the insulating layer 17. The deformation of the shape of the hole 18A is suppressed.

  As a condition for this heat treatment, heat for drying the solution may be applied for a predetermined time in a state where the mold 30 with the solution applied to the convex portion 30A is in contact with the insulating layer 17 on the substrate 12. What is necessary is just to adjust suitably with the composition of a solution, the environment at the time of a manufacturing process, etc.

  Next, as shown in FIG. 6G, the functional layer 20 is formed in the hole 18A of the substrate 12 where the partition wall 18 and the hole 18A are formed by forming the hole 18A in the insulating layer 17. The constituent material is filled. As a method for filling the constituent material of the functional layer 20, an ink jet method is often used. However, the functional layer 20 may be formed in the hole 18A, and is not limited to the ink jet method.

  Next, as shown in FIG. 6H, the organic EL element 10 is manufactured by forming the electrode 16 on the functional layer 20. For the formation of the electrode 16, a vacuum deposition method or the like is used.

  As described above, in the organic EL element 10 of the present embodiment, in the manufacturing process of the organic EL element 10, the insulating material constituting the partition wall 18 is uniformly formed on the substrate 12 on which the electrodes 14 are formed. The insulating layer 17 is formed by coating, and the insulating layer 17 has a projection 30A corresponding to a pattern to be formed and a mold 30 coated with a solution 32 that dissolves the insulating layer 17 in the projection 30A. By contacting, the insulating layer 17 is dissolved. Then, the hole 18A corresponding to the convex portion 30A is formed in the insulating layer 17 by this dissolution, and then the mold 30 is peeled from the substrate 12, thereby patterning the hole 18A delimited by the partition wall 18 (insulating layer 17). To do. For this reason, it is suppressed that the material which comprises the insulating layer 17 mixes in the hole 18A, and it is suppressed that a residue remains in the hole 18A.

  Further, as described above, by making the thickness of the convex portion 30A larger than the thickness of the insulating layer 17, a through hole through which the concave portion corresponding to the convex portion 30A formed in the contact step penetrates the insulating layer 17 in the thickness direction. (Hole 18A) is formed between the electrode 16 and the electrode 14 when the organic EL element 10 is configured by providing the electrode 16 after filling the functional layer 20 in the hole 18A. In addition, the material other than the functional layer 20, the electrode 16, and the electrode 14 is prevented from being mixed between the functional layer 20 and the electrode 16 and the electrode 14, and contact failure is suppressed.

(Second Embodiment)
In the first embodiment, the case where the patterning method of the present embodiment is applied to the fabrication of an organic EL element has been described. However, in the present embodiment, the patterning method is applied to the fabrication of an organic semiconductor transistor. Will be explained.

  As shown in FIG. 7, the organic semiconductor transistor 41 formed in the present embodiment includes a plurality of organic semiconductor transistor elements 40. Each organic semiconductor transistor element 40 includes a source electrode 44, a drain electrode 45, a functional layer 50 provided to be conductive with the source electrode 44 and the drain electrode 45, and an electric field that is insulated from the functional layer 50. And a gate electrode 48 that can be configured. Specifically, the source electrode 44 and the drain electrode 45 are provided on the substrate 42 with a predetermined interval, and the functional layer 50 is provided so as to cover the source electrode 44 and the drain electrode 45. On the functional layer 50, a gate electrode 48 is provided via an insulating layer 46, thereby forming the organic semiconductor transistor element 40.

  As shown in FIG. 7, the organic semiconductor transistor elements 40 are arranged on the same substrate 42 with a predetermined interval, and a partition wall 49 is provided between the organic semiconductor transistor elements 40 to insulate these elements. It has been. The partition walls 49 are formed by patterning holes by the patterning method of the present embodiment (details will be described later). In addition, although the shape of the organic semiconductor transistor element 40 of this invention can be made into a desired shape as needed, it is preferable that it is a thin film form.

  Hereinafter, the configuration and manufacturing method of the organic semiconductor transistor element 40 of the present embodiment will be described in more detail with reference to the drawings.

  As an electrode material used for the source electrode 44, the drain electrode 45, and the gate electrode 48, a material into which charge is efficiently injected is used. Specifically, a metal, a metal oxide, a conductive polymer, or the like is used. The Examples of the metal include magnesium, aluminum, gold, silver, copper, chromium, tantalum, indium, palladium, lithium, calcium, and alloys thereof. Examples of the metal oxide include metal oxide films such as lithium oxide, magnesium oxide, aluminum oxide, indium tin oxide (ITO), tin oxide (NESA), indium oxide, zinc oxide, and indium zinc oxide. Examples of the conductive polymer include polyaniline, polythiophene, polythiophene derivatives, polypyrrole, polypyridine, and a complex of polyethylenedioxythiophene and polystyrene sulfonic acid.

  Note that if the difference in ionization potential between the material used for these electrodes and a polymer compound described later used for the functional layer 50 is large, the charge injection characteristics deteriorate, so that it is used for at least one of the drain electrode 45 and the source electrode 44. The difference between the ionization potential of the obtained material and the polymer compound used for the functional layer 50 is preferably within 1.0 eV, and more preferably within 0.5 eV. In view of the difference in ionization potential between the electrode and the polymer compound, it is particularly preferable to use Au as the electrode material.

  The partition wall 49 and the insulating layer 46 function as an insulating member that insulates between the electrodes (the source electrode 44, the drain electrode 45, and the gate electrode 48) and the gate electrode 48 and the functional layer 50. Inorganic substances such as silicon dioxide, silicon nitride, tantalum oxide, aluminum oxide, titanium oxide, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, cellulose resin, urethane resin, epoxy resin, polystyrene resin, polyvinyl acetate resin Insulating materials such as, but not limited to, styrene butadiene copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, and organic insulating polymers such as silicone resins. It is not something.

  As the functional layer 50, the polymer charge transport material used in the functional layer 20 of the first embodiment is preferably used. Specifically, in the first embodiment, the polymer in the functional layer 20 is used. It is preferable that the repeating unit structure contains at least one selected from the structures represented by the general formulas (I-2) to (I-4) as the charge transporting material, but is not limited thereto. Is not to be done.

As the substrate 42, silicon single crystal or glass doped with phosphorus or the like in high concentration, glass resin, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, cellulose resin, urethane resin, epoxy resin, police styrene resin, polyvinyl Examples include, but are not limited to, acetate resins, styrene butadiene copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, plastic substrates such as silicone resins, and the like. .
In particular, the organic semiconductor transistor element 40 of the present embodiment is used in an electronic circuit used for an electronic device (hereinafter referred to as “flexible electronic device”) that is required to be flexible, such as electronic paper, digital paper, or portable electronic equipment. When using this, it is desirable to use a flexible substrate 42 as the substrate 42. In particular, by using the substrate 42 having a flexural modulus of 1000 MPa or more, more preferably 5000 MPa or more as the substrate 42, the substrate 42 can be applied to a flexible display element driving circuit or electronic circuit.

.
This is because the organic semiconductor transistor element 40 of the present embodiment has sufficient elasticity that the functional layer 50 portion contains the above-described polymer compound as a main component, and is a flexible substrate. This is because even if an element is formed on 42, it can withstand large deformations and repeated deformations and maintain stable performance.

In the present embodiment, the “flexible electronic device” means [1] the usage state is flat regardless of the on / off state of the power supply, such as the electronic paper and digital paper described above. It can be used in a bent state, bent state, bent state, or vice versa. [2] The structure is provided with one or more substrates on the substrate. [3] means an electronic device in which flexibility as described in the above item [1] is required at least in the substrate portion provided with the organic semiconductor transistor element. Further, a protective layer (not shown) may be provided in order to prevent deterioration of the organic semiconductor transistor element 40 due to moisture or oxygen. Specific examples of the protective layer material include metals such as In, Sn, Pb, Au, Cu, Ag, and Al, metal oxides such as MgO, SIO ₂ , and TIO ₂ , polyethylene resins, polyurea resins, and polyimide resins. Resin. For forming the protective layer, a vacuum deposition method, a sputtering method, a plasma polymerization method, a CVD method, or a coating method is applied.

  The organic semiconductor transistor element 40 of the present embodiment described above has an on / off ratio of about 102 to 105 by appropriately selecting the type of polymer compound used in the functional layer 50 portion, the structure of the element, and the like. Within the range, it is adjusted according to the use of the organic semiconductor transistor element.

<Method for manufacturing organic semiconductor transistor element>
A method for manufacturing the organic semiconductor transistor element 40 of the present embodiment will be described.
The organic semiconductor transistor element 40 of this Embodiment is suitably manufactured using the patterning method demonstrated below.

  As described above, in the organic semiconductor transistor element 40 of the present embodiment, in the manufacturing process, as shown in FIG. 8, the partition wall 49 is formed on the substrate 42 on which the source electrode 44 and the drain electrode 45 are formed. The insulating material 47 is uniformly applied to form the insulating layer 47, and the insulating layer 47 has a convex portion 60A corresponding to the pattern to be formed and dissolves the insulating layer in the convex portion 60A. After the insulating layer 47 is dissolved to form a hole 49A corresponding to the convex portion 60A, the mold 60 is peeled from the substrate 42 to pattern the hole 49A. . As a result, a hole 49 </ b> A for filling the functional layer 50 is formed in the insulating layer 47. Then, after the functional layer 50 is formed by filling the formed hole 49A with the material constituting the functional layer 50, the insulating layer 60 and the gate electrode 48 are provided. Details will be described below.

  As shown in FIG. 8A, first, a substrate 42 provided with a source electrode 44 and a drain electrode 45 is prepared. Then, as shown in FIG. 8B, an insulating layer 47 that finally functions as the partition wall 49 is formed by uniformly applying the insulating material for forming the partition wall 49 onto the substrate 42. Form. As this insulating material, a material having excellent insulating properties and satisfying a good film forming condition is used, and it is hardly soluble in a material that dissolves in a solution to be described later and forms the functional layer 50. Any material may be used as long as it satisfies the property of being.

  The definitions of terms used in the present embodiment, such as “soluble in a solution”, “slightly soluble in a solution”, and “good film forming conditions”, are the same as those in the first embodiment. Since they are the same, detailed description is omitted.

  As a method of applying this insulating material onto the substrate 42, methods such as spin coating, dipping, and casting may be used, and various methods such as ink jet, printing, and barcode may be used. Not limited to.

  Next, a mold 60 having a convex portion 60A corresponding to a pattern to be formed on the insulating layer 47 (in the present embodiment, a hole for forming the functional layer 50) is prepared. Next, a solution is applied to the convex portion 60A of the mold 60 (FIG. 8C). The mold 60 is made of a metal material having a low elastic modulus in accordance with the elastic modulus of the pattern formation target layer (insulating layer 47 in the present embodiment), the ease of patterning, or the like. Alternatively, a material made of an elastic material may be used.

In the present embodiment, it is assumed that the thickness of the convex portion 60 </ b> A formed on the mold 60 is adjusted to be larger than the thickness of the insulating layer 47 formed on the substrate 42.
By adjusting the thickness of the convex portion 60A to be larger than the thickness of the insulating layer 47, in a process described later, the concave portion formed in the insulating layer 47 according to the convex portion 60A causes the insulating layer 47 to move in the thickness direction. It is formed as a through hole (hole 49A) that penetrates.

  In the present embodiment, a through-hole penetrating the insulating layer 47 is provided by the mold 60 in which the convex portion 60A is formed, and the functional layer 50 is filled with a later-described functional layer 50 so that the functional layer 50 becomes the source electrode. 44 and the drain electrode 45 are preferably in contact with each other. Therefore, the thickness of the convex portion 60A is adjusted in advance to be larger than the thickness of the insulating layer 47. For example, a non-penetrating concave portion is simply provided in the insulating layer 47. Needless to say, the thickness of the recess 60 </ b> A may be less than the thickness of the insulating layer 47.

  Then, a solution for dissolving the insulating layer 47 is applied to the convex portions 60A of the mold 60 in the same manner as in the first embodiment.

When the casting solution 60 is brought into contact with the insulating layer 47 in a process to be described later, the solution is applied to the region on the casting layer 60 where the dissolving solution is applied (the pattern is to be provided with a recess on the insulating layer 47). Application may be made so as to be in contact with a region to be formed).
For this reason, when a pattern corresponding to the convex portion 60A of the mold 60 is formed on the insulating layer 47, the solution is applied only to the region to be patterned when the mold 60 is brought into contact with the insulating layer 47. That's fine.

  In the present embodiment, the case where the solution is applied only to the convex portion 60A will be described. However, as in the first embodiment, the thickness of the convex portion 60A of the mold 60 is larger than the thickness of the insulating layer 47. In the case where adjustment is performed, since the region to be contacted is only the convex portion 60A when the mold 60 is brought into contact with the insulating layer 47, the application of the solution is performed on the region other than the convex portion 60A. You can go. In this way, the solution can be easily applied by a simple process.

  As the solution, a material that forms the insulating layer 47 is dissolved, and a material that forms the source electrode 44 and the drain electrode 45 may be a hardly soluble material, depending on the material that forms the insulating layer 47. Determined. Examples of the solution include the solution used in the first embodiment, but are not limited thereto as long as the above characteristics are satisfied.

  Further, as in the first embodiment, the lyophilic treatment is performed on the region (the projecting portion 60A in the present embodiment) to which the dissolution liquid 62 of the mold 60 is applied, and then the dissolution liquid 62 is applied. Is preferably applied. By applying the solution 62 after the surface of the mold 60 has been made lyophilic, the solution 62 may dripping from the mold 60 or the thickness of the solution 62 applied to the mold 60 may be uneven. Things are suppressed. As a method for this lyophilic treatment, the same method as in the first embodiment can be cited, and thus the description is omitted.

Further, similar to the solution used in the first embodiment, this solution preferably contains various solid components dispersed or contained for viscosity adjustment for suppressing dripping from the mold 60. May be. The solid component may be any material as long as it is used for viscosity adjustment and does not affect the electrical characteristics of the surroundings. Preferably, the insulating layer 47 to be dissolved is formed. It is preferable to include the same material as the material to be processed. By including the material constituting the insulating layer 47 as a solid component, even if a part of the solution remains in the hole or the recess formed in the insulating layer 47, the function deterioration as an element is suppressed. The
Since the content of the solid component contained in the solution is the same as that in the first embodiment, description thereof is omitted.

  Next, at least the casting mold 60 with the solution 62 applied to the convex portion 60A is brought into contact with the substrate 42 so that the side on which the convex portion 60A is formed contacts the insulating layer 47 (FIG. 8D, FIG. E) Contact process).

  In this contact step, the region where the solution of the convex portion 60A of the mold 60 is applied comes into contact, so that the region in contact with the solution applied on the convex portion 60A of the entire region of the insulating layer 47 is formed. Dissolved. For this reason, when the mold 60 is peeled from the substrate 42 (see FIG. 8F), the insulating layer 47 is provided with holes 49A corresponding to the convex portions 60A and the holes formed in the insulating layer 47. As a result, a partition wall 49 made of an insulating material is formed by the portion 49A (see FIG. 8F).

  In this contact step, as in the first embodiment, the mold 60 is used to dissolve the insulating layer 47 with high efficiency and effectively to form the hole 49A corresponding to the convex portion 60A. It is preferable to dry the solution by performing heat treatment in contact with the substrate 42. In this contact step before the mold 60 is peeled from the substrate 42, heat treatment is performed and the solution is dried, so that an undried solution remains at the interface with the insulation layer 47, thereby forming the insulating layer 47. The deformation of the hole 49A is suppressed.

  As a condition for this heat treatment, heat for drying the solution may be applied for a predetermined time in a state where the mold 60 with the solution applied to the convex portion 60A is in contact with the insulating layer 47 on the substrate 42. What is necessary is just to adjust suitably with the composition of a solution, the environment at the time of a manufacturing process, etc.

  Next, as shown in FIG. 8G, the functional layer 50 is formed in the hole 49A of the substrate 42 in which the partition wall 49 and the hole 49A are formed by forming the hole 49A in the insulating layer 47. The constituent material is filled. As a method of filling the constituent material of the functional layer 50, an ink jet method is often used. However, the functional layer 50 may be formed in the hole 49A, and is not limited to the ink jet method.

  Next, as shown in FIG. 8H, after the insulating layer 46 is formed on the functional layer 20 by applying the insulating material in the same manner as in the formation of the insulating layer 47, the structure shown in FIG. The organic semiconductor transistor 41 provided with the plurality of organic semiconductor transistor elements 40 is formed by forming the gate electrode 48 as shown in FIG. The gate electrode 48 may be formed by using a vacuum vapor deposition method or the like.

  As described above, in the organic semiconductor transistor 41 of the present embodiment, in the manufacturing process, the insulating material constituting the partition wall 49 is uniformly formed on the substrate 42 on which the source electrode 44 and the drain electrode 45 are formed. The insulating layer 47 is formed by coating, and the insulating layer 47 has a projection 60A corresponding to the pattern to be formed and a mold 60 coated with a solution 62 that dissolves the insulating layer 47 in the projection 60A. By contacting, the insulating layer 47 is dissolved. Then, holes 49A corresponding to the projections 60A are formed in the insulating layer 47 by this dissolution, and then the mold 60 is peeled from the substrate 42, thereby patterning the holes 49A delimited by the partition walls 49 (insulating layer 47). To do. For this reason, it is suppressed that the material which comprises the insulating layer 47 mixes in the hole 49A, and it is suppressed that a residue generate | occur | produces in the hole 47A.

  Further, as described above, by making the thickness of the convex portion 60A larger than the thickness of the insulating layer 47, a through hole in which the concave portion corresponding to the convex portion 60A formed in the contact step penetrates the insulating layer 47 in the thickness direction. Since the hole 49A is filled with the functional layer 50 and then the insulating layer 46 and the gate electrode 48 are provided to form the organic semiconductor transistor element 40, the source electrode 44 and the drain Materials other than the functional layer 50, the source electrode 44, and the drain electrode 45 may be mixed between the functional layer 50 between the electrode 45 and the source electrode 44 and the drain electrode 45. It is suppressed and contact failure is suppressed.

  In the first and second embodiments, the case where the patterning method of the present embodiment is applied to the manufacture of an organic EL element and an organic semiconductor transistor element has been described. The patterning method according to the embodiment may be applied to any application as long as patterning is performed by forming a recess or a hole. In particular, in order to form a functional layer between the electrodes, a concave portion or a hole for filling the functional layer is formed, or a concave portion or a hole is provided in a region other than the region to be a partition for providing the partition. The present invention is applicable to cases and the like, and is not limited to the above embodiment.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

(Example A1)
An insulating layer having a thickness of 300 nm is uniformly formed by spin coating using a 3.0 mass% tetralin solution of a cycloolefin polymer on a glass substrate on which a 2 mm-wide strip-shaped ITO electrode that has been washed and dried is etched. And dried well. Next, a mold having a convex portion (thickness of the convex portion 100 μm, convex shape: columnar shape of 20 μm × 20 μm, and a convex portion having a thickness of 500 μm other than the convex portion, tetralin is immersed as a solution in the immersion method. Applied.

  Next, while aligning manually with a CCD camera, the mold is overlaid on the insulating layer formed on the glass substrate so that the convex portion coated with the dissolving solution contacts, A hole corresponding to the convex portion was formed by applying a strong pressure. Then, with the mold superimposed on the glass substrate, the solution was dried by leaving it in an environment of 25 ° C. and 40% RH for 1 hour, and then the mold was peeled from the glass substrate. When the surface of the glass substrate was visually confirmed, a hole corresponding to the convex portion of the mold (depth of the hole 300 nm, shape of the hole: columnar shape of 20 μm × 20 μm) was formed in the insulating layer.

Next, a polyfluorene-based light-emitting material (in the exemplary compound (II-16), where n = 8 and y = 0, Mw 1.8 × 10 ⁻⁶ ) is used as a functional layer in the formed hole. A 2.0 mass% 1,2,4 trimethylbenzene solution was filled using an inkjet method. Thereby, a functional layer as a light emitting portion having a thickness of 80 nm was formed. Further, an organic EL element A1 was produced by forming Ca / Al with a thickness of 30 nm and 200 nm, respectively, on this functional layer by vacuum deposition.

(Example A2)
Insulation with a thickness of 300 nm by spin coating using a 3.0 mass% 1,2,4 trichlorobenzene solution of polyimide on a glass substrate formed by etching a 2 mm wide strip-shaped ITO electrode that has been washed and dried. The layer was formed uniformly and dried thoroughly. Next, a mold having a convex portion (thickness of the convex portion 100 μm, shape of the convex portion: 20 μm × 20 μm columnar shape, thickness of the portion other than the convex portion 500 μm) is prepared, and on the side where the convex portion is formed The surface of the mold was made lyophilic by performing UV ozone treatment on the surface for 10 minutes using a UV ozone cleaner (UV42, manufactured by Nippon Laser Electronics Co., Ltd.).

  Next, 1,2,4 trichlorobenzene was applied as a solution to the convex portion of the mold, which was made lyophilic, using a dipping method.

  Next, while aligning manually with a CCD camera, the mold is overlaid on the insulating layer formed on the glass substrate so that the convex portion coated with the dissolving solution is in contact with it, and a convex is applied by applying pressure. A hole corresponding to the portion was formed. Then, with the mold superimposed on the glass substrate, the solution was dried by leaving it in an environment of 25 ° C. and 40% RH for 1 hour, and then the mold was peeled from the glass substrate. When the surface of the glass substrate was visually confirmed, a hole corresponding to the convex portion of the mold (depth of the hole 300 nm, shape of the hole: columnar shape of 20 μm × 20 μm) was formed in the insulating layer.

  Next, a 2.0 mass% 1,2,4 trimethylbenzene solution of the same polyfluorene-based luminescent material as in Example A1 was filled in the formed hole portion as a functional layer using an ink jet method. Thereby, a functional layer as a light emitting portion having a thickness of 80 nm was formed. Further, an organic EL element A2 was produced by forming Ca / Al with a thickness of 30 nm and 200 nm on the functional layer by vacuum deposition, respectively.

(Example A3)
Spin coating using a 2.0 mass% 1,2,4 trichlorobenzene solution of PMMA (polymethylmethacrylate) on a glass substrate on which a 2 mm wide strip-shaped ITO electrode that has been washed and dried is etched. Thus, an insulating layer having a thickness of 100 nm was uniformly formed and sufficiently dried. Next, a mold having a convex portion (thickness of the convex portion 100 μm, shape of the convex portion: 20 μm × 20 μm columnar shape, thickness of the portion other than the convex portion 500 μm) is prepared, and the side where the convex portion is formed The surface of the mold was made lyophilic by performing UV ozone treatment on the surface for 10 minutes using a UV ozone cleaner (UV42, manufactured by Nippon Laser Electronics Co., Ltd.).

  Next, 1,2,4 trichlorobenzene was applied as a solution to the convex portion of the mold, which was made lyophilic, using a dipping method.

  Next, while aligning manually with a CCD camera, the mold is placed on the insulating layer formed on the glass substrate so that the convex part coated with the solution is in contact with the mold, and pressure is applied by applying pressure. A hole corresponding to the portion was formed. Then, the mold was peeled off from the glass substrate after being heat-treated by being left standing in an environment of 130 ° C. and 40% RH for 10 minutes in a state where the mold was superimposed on the glass substrate. When the surface of the glass substrate was visually confirmed, a hole corresponding to the convex portion of the mold (depth of the hole 300 nm, shape of the hole: columnar shape of 20 μm × 20 μm) was formed in the insulating layer.

  Next, a 2.0 mass% 1,2,4 trimethylbenzene solution of the same polyfluorene-based luminescent material as in Example A1 was filled in the formed hole portion as a functional layer using an ink jet method. Thereby, a functional layer as a light emitting portion having a thickness of 80 nm was formed. Further, an organic EL element A3 was produced by forming Ca / Al with a thickness of 30 nm and 200 nm, respectively, on the functional layer by vacuum deposition.

(Comparative Example A1)
A comparative organic EL element A1 was produced in the same manner as in Example A1, except that the hole formed in the insulating layer in Example A1 was formed using an inkjet method.
Specifically, the ink prepared in Example A1 is applied to the solution prepared in Example A1 on the insulating layer formed on the glass substrate by the same method as in Example A1, using an inkjet discharge device (trade name: DMP-2831 manufactured by Dimatix). Was discharged. The discharge amount was 10 pl × 5 drops per location.
When the surface of the insulating layer of the glass substrate on which the dissolved solution was discharged was visually confirmed, a hole (a hole depth of 300 nm, a hole shape: a cylindrical shape with a diameter of 60 μm) was formed in the insulating layer. It was.

  Next, a 2.0 mass% 1,2,4 trimethylbenzene solution of the same polyfluorene-based light-emitting material as that of Example A1 as a functional layer is inkjetted into the formed hole by the same method as Example A1. Filled using the method. Thereby, a functional layer as a light emitting portion having a thickness of 80 nm was formed. Furthermore, comparative organic EL element A1 was produced by forming Ca / Al with a thickness of 30 nm and 200 nm, respectively, on this functional layer by vacuum deposition.

(Comparative Example A2)
A comparative organic EL element A2 was produced in the same manner as in Example A2, except that the hole formed in the insulating layer in Example A2 was formed by the same method and conditions as in Comparative Example A1 using the inkjet method.

(Comparative Example A3)
A comparative organic EL element A3 was produced in the same manner as in Example A3 except that in Example A3, the hole formed in the insulating layer was formed by the same method and conditions as in Comparative Example A1 using the inkjet method.

-Evaluation-
With respect to the organic EL element produced as described above, the uniformity of the formed partition, the residue due to the insulating material in the hole (functional layer), and the functioned pixel were evaluated.

―Evaluation of partition wall uniformity―
Whether or not a hole corresponding to the convex portion of the mold is formed for a partition formed by providing a hole in the insulating layer (a region other than the hole in the insulating layer, that is, a partition between the holes). I evaluated it. The evaluation criteria are as follows. The evaluation results are shown in Table 1.
The shape and depth of the hole provided in the insulating layer were measured using a laser microscope (manufactured by Keyence, VK-9700).

G1: The partition walls are uniformly formed, and the partition walls having a uniform shape, position, and size are formed by forming holes corresponding to the shape, position, and size of the convex portions of the mold.
G2: There is a portion where a part of the partition wall is observed to sag into the hole, or the partition wall position is shifted (displaced) from the position of the convex portion of the mold.
G3: No partition is formed.

-Residue evaluation in the hole-
The following evaluation was performed about the residue of the hole. The evaluation criteria are as follows, and the residue was evaluated by visual inspection using an optical microscope (Olympus, GX71). The evaluation results are shown in Table 1.

G1: No residue G2: A residue is seen around the hole.
G3: A residue is seen over the entire surface.

―Evaluation of functional pixels―
For the produced organic EL element, a DC voltage was applied in vacuum (133.3 × 10 ⁻³ Pa (10 ⁻³ Torr)) with the electrode side provided on the substrate side being positive and the opposite electrode side being negative. Emission is performed in the same manner as the residue evaluation, with the percentage of functioning pixels as the percentage of the light-emitting area of the plurality of functional layers (that is, the light-emitting area) formed with respect to the entire area of the functional layer. The state was magnified with an optical microscope (Olympus, GX71), and the light emission area was calculated. The evaluation results are shown in Table 1. When the ratio of the functioning area exceeds 95%, there is no contact failure between the electrode and the functional layer, and the residue of the insulating material remains in the hole filled with the functional layer. I can say no.

―Drive evaluation―
About the produced organic EL element, while applying a DC voltage in vacuum (133.3 × 10 ⁻³ Pa (10 ⁻³ Torr)), the electrode side provided on the substrate side is positive and the opposite electrode side is negative. The applied voltage was gradually increased to evaluate the voltage (rising voltage) at which the plurality of formed functional layers start to emit light, the device life, and the light emission state. The evaluation results are shown in Table 2.
The device life is evaluated by adjusting the current value so that the initial luminance is 100 cd / m ^2, and the time from when the luminance exceeds the initial luminance by constant current driving until it is halved as the device lifetime (hours). It was measured. The evaluation results are shown in Table 2.

  The light emission state was evaluated by observing the light emitting surface in an enlarged manner and visually observing light emission unevenness. The evaluation criteria are as follows. The evaluation results are shown in Table 2.

G1: Good because the light emission state is uniform over the entire surface.
G2: The light emission state is uneven and uneven.
G3: Does not emit light.

  As shown in Table 1 and Table 2, Examples A1 to A3, in which organic EL elements were produced by forming holes by the pattern forming method of this example, were Comparative Examples A1 to A1 in which holes were formed by the inkjet method. Compared with A3, no residue was found in the hole, and good results were obtained in all evaluation items of partition uniformity, functioning pixels, rising voltage, lifetime, and light emitting state. For this reason, if the pattern forming method of this embodiment is used, the residue remaining in the hole formed by pattern formation is suppressed, and a uniform and suitable pattern can be easily formed in a short time. It can be said. Further, in Examples A1 to A3, it can be said that the contact failure between the electrode and the functional layer is also suppressed.

(Example B1)
A metal mask was placed on the glass substrate, gold was deposited to a thickness of 100 nm, and a source electrode and a drain electrode were provided. An insulating layer having a thickness of 300 nm was uniformly formed on this substrate by spin coating using a 3.0% by mass tetralin solution of a cycloolefin polymer and sufficiently dried. Next, tetralin as a solution is immersed in the convex portion of the mold having the convex portion (thickness of the convex portion 100 μm, convex shape: column shape of 20 μm × 200 μm, thickness of the portion other than the convex portion 500 μm). It was applied using the method.

  Next, while aligning manually with a CCD camera, the convex part is formed by applying pressure by overlaying the mold so that the convex part coated with the solution is in contact with the insulating layer formed on the glass substrate. The hole part corresponding to was formed. Then, with the mold superimposed on the glass substrate, the solution was dried by leaving it in an environment of 25 ° C. and 40% RH for 1 hour, and then the mold was peeled from the glass substrate. When the surface of the glass substrate was visually confirmed, holes (depth of hole: 300 nm, shape of hole: column shape of 20 μm × 200 μm) corresponding to the convex portions of the mold were formed in the insulating layer.

Next, 2.0 mass of the polymer material (Exemplary Compound (I-1), Mw1.4 × 10 ⁻⁶ ) shown in the first embodiment as a functional layer in the formed hole. % 1,2,4 trimethylbenzene solution was filled using the inkjet method. As a result, a functional layer having a thickness of 80 nm was formed. Furthermore, an insulating layer having a thickness of 100 nm is uniformly formed on this functional layer by spin coating using a 3.0 mass% tetralin solution of a cycloolefin polymer, and the insulating layer is formed by sufficiently drying. Subsequently, an organic semiconductor transistor element B1 was produced by forming a gate electrode by depositing Al with a film thickness of 200 nm by a vacuum deposition method.

(Example B2)
A metal mask was placed on the glass substrate, gold was deposited to a thickness of 100 nm, and a source electrode and a drain electrode were provided. On this substrate, an insulating layer having a thickness of 300 nm was uniformly formed by spin coating using a 1,2,4 trichlorobenzene solution of 3.0% by mass of polyimide and sufficiently dried. Next, a mold having a convex portion (thickness of the convex portion of 100 μm, shape of the convex portion: columnar shape of 20 μm × 200 μm, thickness of the portion other than the convex portion of 500 μm) is prepared, and on the side where the convex portion is formed The surface of the mold was made lyophilic by performing UV ozone treatment on the surface for 10 minutes using a UV ozone cleaner (UV42, manufactured by Nippon Laser Electronics Co., Ltd.).

  Next, 1,2,4 trichlorobenzene was applied as a solution to the convex portion of the mold having the surface made lyophilic using a dipping method.

  Next, while aligning manually with a CCD camera, the convex part is formed by applying pressure by overlaying the mold so that the convex part coated with the solution is in contact with the insulating layer formed on the glass substrate. The hole part corresponding to was formed. Then, with the mold superimposed on the glass substrate, the solution was dried by leaving it in an environment of 25 ° C. and 40% RH for 1 hour, and then the mold was peeled from the glass substrate. When the surface of the glass substrate was visually confirmed, holes (depth of hole: 300 nm, shape of hole: column shape of 20 μm × 200 μm) corresponding to the convex portions of the mold were formed in the insulating layer.

Next, 2.0 mass of the polymer material (Exemplary Compound (I-1), Mw1.4 × 10 ⁻⁶ ) shown in the first embodiment as a functional layer in the formed hole. % 1,2,4 trimethylbenzene solution was filled using the inkjet method. As a result, a functional layer having a thickness of 80 nm was formed. Furthermore, an insulating layer having a thickness of 100 nm is uniformly formed on this functional layer by spin coating using a 3.0 mass% tetralin solution of a cycloolefin polymer, and the insulating layer is formed by sufficiently drying. Thereafter, an organic semiconductor transistor element B2 was fabricated by forming a gate electrode by depositing Al with a film thickness of 200 nm by a vacuum deposition method.

(Example B3)
A metal mask was placed on the glass substrate, gold was deposited to a thickness of 100 nm, and a source electrode and a drain electrode were provided. On this substrate, an insulating layer having a thickness of 300 nm was uniformly formed by spin coating using a 1,2,4 trichlorobenzene solution of 3.0% by mass of polyimide and sufficiently dried. Next, a mold (convex thickness 100 μm, convex shape: column shape of 20 μm × 200 μm, thickness other than the convex part 500 μm) on which the convex part is formed is prepared. The surface of the mold was made lyophilic by performing UV ozone treatment on the surface for 10 minutes using a UV ozone cleaner (UV42, manufactured by Nippon Laser Electronics Co., Ltd.).

  Next, 1,2,4 trichlorobenzene was applied as a solution to the convex portion of the mold, which was made lyophilic, using a dipping method.

  Next, while aligning manually with a CCD camera, the mold is placed on the insulating layer formed on the glass substrate so that the convex part coated with the solution is in contact with the mold, and pressure is applied by applying pressure. A hole corresponding to the portion was formed. Then, the mold was peeled off from the glass substrate after being heat-treated by being left standing in an environment of 130 ° C. and 40% RH for 10 minutes in a state where the mold was superimposed on the glass substrate. When the surface of the glass substrate was visually confirmed, holes (depth of hole: 300 nm, shape of hole: column shape of 20 μm × 200 μm) corresponding to the convex portions of the mold were formed in the insulating layer.

Next, 2.0 mass of the polymer material (Exemplary Compound (I-1), Mw1.4 × 10 ⁻⁶ ) shown in the first embodiment as a functional layer in the formed hole. % 1,2,4 trimethylbenzene solution was filled using the inkjet method. As a result, a functional layer having a thickness of 80 nm was formed. Furthermore, an insulating layer having a thickness of 100 nm is uniformly formed on this functional layer by spin coating using a 3.0 mass% tetralin solution of a cycloolefin polymer, and the insulating layer is formed by sufficiently drying. Thereafter, an organic semiconductor transistor element B3 was fabricated by forming a gate electrode by depositing Al with a film thickness of 200 nm by a vacuum deposition method.

(Comparative Example B1)
A comparative organic semiconductor transistor element B1 was produced in the same manner as in Example B1, except that the hole formed in the insulating layer in Example B1 was formed using an inkjet method.
Specifically, the ink prepared in Example B1 was applied to the solution prepared in Example B1 on the insulating layer formed on the glass substrate by the same method as in Example B1, using an inkjet discharge device (trade name: DMP-2831). And discharged. The discharge amount was 10 pl × 5 drops per location.
When the surface of the insulating layer of the glass substrate on which the dissolved solution was discharged was visually confirmed, a hole (a hole depth of 300 nm, a hole shape: a cylindrical shape with a diameter of 60 μm) was formed in the insulating layer. It was.

Then, the hole that is this formation, example in the same manner as B1, polymeric materials indicated as a functional layer in the first embodiment (exemplary compound (I-1), Mw1.4 × 10 - ⁶ ) The 2.0 mass% 1,2,4 trimethylbenzene solution of ⁶ ) was filled using the inkjet method. Thereby, a functional layer as a light emitting portion having a thickness of 80 nm was formed. Furthermore, an insulating layer having a thickness of 100 nm is uniformly formed on this functional layer by spin coating using a 3.0 mass% tetralin solution of a cycloolefin polymer, and the insulating layer is formed by sufficiently drying. Then, comparative organic semiconductor transistor element B1 was produced by forming a gate electrode by depositing Al with a film thickness of 200 nm by a vacuum deposition method.

(Comparative Example B2)
In Comparative Example B2, a comparative organic semiconductor transistor element B2 was produced in the same manner as in Example B2, except that the hole formed in the insulating layer was formed by the same method and conditions as in Comparative Example B1 using the inkjet method. .

(Comparative Example B3)
In Comparative Example B3, a comparative organic semiconductor transistor element B3 was produced in the same manner as in Example B3, except that the hole formed in the insulating layer was formed by the same method and conditions as in Comparative Example B1 using the inkjet method. .

-Evaluation-
Regarding the organic semiconductor transistor element manufactured as described above, the time required for manufacturing the element (tact time), the uniformity of the partition wall formed, the residue due to the insulating material in the hole (functional layer), the function element Each was evaluated.

―Evaluation of partition wall uniformity―
Whether or not a hole corresponding to the convex portion of the mold is formed for a partition formed by providing a hole in the insulating layer (a region other than the hole in the insulating layer, that is, a partition between the holes). A visual evaluation was performed. The evaluation criteria are as follows. The evaluation results are shown in Table 3.

G1: The partition walls are uniformly formed, and the partition walls having a uniform shape, position, and size are formed by forming holes corresponding to the shape, position, and size of the convex portions of the mold.
G2: There is a portion where a part of the partition wall is observed to sag into the hole, or the partition wall position is shifted (displaced) from the position of the convex portion of the mold.
G3: No partition is formed.

-Residue evaluation in the hole-
The following evaluation was performed about the residue of the hole. The evaluation criteria are as follows, and the residue was evaluated by visual inspection using an optical microscope (Olympus, GX71). The evaluation results are shown in Table 3.

G1: No residue G2: A residue is seen around the hole.
G3: A residue is seen over the entire surface.

―Evaluation of functional devices―
With respect to the produced organic semiconductor transistor element, the current between the source and drain when a gate voltage (20 V) was applied was measured, and the case where the current was measured (current flowed) was defined as “functioning”. ) Was evaluated, and the ratio of functioning elements among a plurality of elements formed on the same substrate was evaluated. The evaluation results are shown in Table 3. When the ratio of the functioning elements exceeds 95%, there is no contact failure between the electrode and the functional layer, and the residue of the insulating material remains in the hole filled with the functional layer. I can say no.

―Drive evaluation―
Using the semiconductor parameter analyzer (Agilent Technology Co., Ltd., 4155C), measured the current-voltage characteristics when the gate voltage was applied to the prepared organic semiconductor transistor element, and the carrier mobility (linear region) and the on / off ratio were determined. Calculated. The calculation results are shown in Table 4.

  As shown in Tables 3 and 4, Examples B1 to B3, in which organic semiconductor transistor elements were formed by forming holes by the pattern forming method of this example, were comparative examples B1 in which holes were formed by the inkjet method. Compared to ˜B3, no residue was found in the hole, and good results were obtained in all evaluation items of the uniformity of the partition walls and the functioning pixels. Moreover, also about the on / off ratio of the organic-semiconductor transistor element, Example B-B3 obtained the favorable result compared with comparative example B1-B3. For this reason, if the pattern forming method of this embodiment is used, the residue remaining in the hole formed by pattern formation is suppressed, and a uniform and suitable pattern can be easily formed in a short time. It can be said. In Examples B1 to B3, it can be said that the contact failure between the source and drain electrodes and the functional layer is also suppressed.

It is a schematic cross section which shows an example of the organic EL element produced using the patterning method of this invention. It is a schematic cross section which shows an example of the total attack of a functional layer. It is a schematic cross section which shows an example of the total attack of a functional layer. It is a schematic cross section which shows an example of the total attack of a functional layer. It is a schematic cross section which shows an example of the total attack of a functional layer. (A)-(H) It is a schematic diagram which shows the manufacture process of the organic EL element produced using the patterning method of this invention. It is a schematic diagram which shows an example of the organic-semiconductor transistor element produced using the patterning method of this invention. (A)-(I) It is a schematic diagram which shows an example of the organic-semiconductor transistor element produced using the patterning method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Organic EL element 12 Substrate 14 Electrode 16 Electrode 17 Insulating layer 20 Functional layer 40 Organic semiconductor transistor element 41 Organic semiconductor transistor 42 Substrate 44 Source electrode 45 Drain electrode 46 Insulating layer 47 Insulating layer 48 Gate electrode 49 Partition 49A Hole 50 Functional layer 60 Insulating layer

Claims (11)

An application step of applying a solution for dissolving the pattern formation target layer to the convex portion of the mold having a convex portion corresponding to the pattern to be formed;
A contact step of bringing the mold into contact with the pattern formation target layer from a side of the mold on which the lysing solution is applied;
A peeling step of peeling the mold from the pattern formation target layer in which a concave portion or a hole portion corresponding to the convex portion is formed by dissolution with the dissolving solution;
I have a,
The patterning method whose thickness of the said convex part is larger than the thickness of the said pattern formation object layer . The patterning method according to claim 1 , wherein in the coating step, the solution is applied over the entire surface of the mold on the side where the convex portions are formed. 3. The application step according to claim 1 or 2 , wherein in the application step, the solution is applied after the region of the mold to which the solution is applied is made lyophilic with respect to the solution. The patterning method as described. The patterning method according to claim 1 , wherein, in the contacting step, the mold is brought into contact with the pattern formation target layer, and then heated and dried. The patterning method according to claim 1 , wherein the mold is made of metal. The patterning method according to claim 1 , wherein the mold has elasticity. The patterning method according to claim 1, wherein the solution contains a solid component. The patterning method according to claim 7 , wherein the solid component is a material constituting the pattern formation target layer. A pair of electrodes, a functional part formed between the pair of electrodes and composed of one or a plurality of organic compound layers, and a partition member that divides the functional part into a plurality of regions,
At least one of the pair of electrodes is composed of one or a plurality of electrode groups,
It said partition member is a pattern formation target layer formed of the hole by the patterning method according to any one of claims 1 to 8,
The functional unit, the one or a plurality of organic compound layers is filled into a hole formed in pattern formation target layer by the patterning method according to any one of claims 1 to 8 Organic electric element formed by. A pair of electrodes, a light emitting part formed between the pair of electrodes and composed of one or more organic compound layers, and a partition member that divides the light emitting part into a plurality of regions,
At least one of the pair of electrodes is composed of one or a plurality of electrode groups,
It said partition member is a pattern formation target layer formed of the hole by the patterning method according to any one of claims 1 to 8,
The light emitting unit, the one or a plurality of organic compound layers is filled into a hole formed in pattern formation target layer by the patterning method according to any one of claims 1 to 8 Organic electroluminescent device formed by A source electrode, a drain electrode, a functional part configured by an organic semiconductor layer provided to be conductive with the source electrode and the drain electrode, and a gate electrode insulated from the functional part and applied with an electric field; A plurality of organic semiconductor transistor elements including a partition member that insulates between the organic semiconductor transistor elements,
The partition wall member is a pattern formation target layer formed of the hole by the patterning method according to any one of claims 1 to 8,
The organic semiconductor transistor formed by filling the organic semiconductor layer in the hole formed in the pattern formation target layer by the patterning method according to claim 1. .

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