JP2012146444A - Organic electronics device manufacturing method and organic electronics device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for an organic electronics device which excels in reproducibility of high-definition pattern printing where low-viscosity ink is used for printing and also can form especially an organic electronics layer in even thickness up to the very end thereof thanks to high film thickness uniformity of an organic electronics layer, and an organic electronics device manufactured thereby.SOLUTION: The organic electronics device manufacturing method comprises a step in which a patterned substrate 10 is fabricated which has formed thereon a pattern consisting of a liquid-repellent part 12a exhibiting liquid repellent property against a solvent contained in an ink for forming an organic electronics layer 30 and a lyophilic part 11a exhibiting lyophilic property for the solvent; a step in which a coating of the ink is applied to a blanket 22 to form the organic electronics layer 30; and a step in which the organic electronics layer 30 is contacted with the patterned substrate 10 to make the organic electronics layer 30 transferred to the lyophilic part 11a.

Description

  The present invention relates to a method for producing an organic electronic device such as an organic transistor or organic electroluminescence, and an organic electronic device.

  Organic electroluminescence (organic EL), which is one of organic electronic devices, is composed of a plurality of laminated structures in which an organic light emitting medium layer having an organic light emitting layer and an organic light emitting auxiliary layer is disposed between a pair of electrodes. Light is emitted when a current flows through the light emitting medium layer. In order to efficiently emit light from the organic EL, it is important to control the film thickness of the organic light emitting medium layer, and it is necessary to make the film thickness as thin as about 10 to 100 nm (nanometers). Furthermore, in order to make an organic EL display, it is necessary to pattern the material for forming the organic light emitting medium layer on the substrate with high definition. Thus, in the manufacture of organic EL, a process that can achieve both the thinning of the organic light emitting medium layer and the formation of a high-definition pattern is required. Similar techniques are also required in the formation of organic semiconductor layers of organic transistors.

  The patterning of the material forming the organic light emitting medium layer has so far been performed by resistance heating vapor deposition (vacuum vapor deposition) using a fine pattern metal mask. However, this method has a problem that patterning accuracy is less likely to occur as the substrate becomes larger.

On the other hand, recently, a method of forming a thin film by applying a coating ink solution in which a material for forming an organic light emitting medium layer is dissolved in a solvent onto a substrate by a wet coating method has been performed. Examples of the wet coating method include a spin coating method, a bar coating method, a discharge coating method, and a dip coating method.
However, it is difficult for the wet coating method to perform patterning with high definition or to separate the three colors of red (R), green (G), and blue (B). For these high-definition pattern formation and coating patterning, thin film formation by a pattern printing method is effective.

In an organic EL element or an organic EL display, a glass substrate is frequently used as a substrate. Therefore, in the production of organic EL, a method using a hard printing plate made of metal or ceramic such as gravure printing is not suitable.
As a pattern printing method suitable for the production of organic EL, a printing method using a rubber printing plate having elasticity, an offset printing method using a rubber printing blanket (see, for example, Patent Document 1), and elasticity. A letterpress printing method or intaglio printing method using a photosensitive resin plate mainly composed of rubber or other resin (see, for example, Patent Document 2), or an ink jet printing method in which a coating ink liquid is driven into a predetermined area of a pattern (for example, a patent) Reference 3) can be employed.
Further, a reverse offset printing method has been proposed in which an ink containing an organic light emitting material and a solvent is applied on a silicone blanket to form an organic electronics layer pattern, and then transferred to a substrate (see Patent Document 4). . According to the reverse offset printing method, the organic electronics layer is dried to some extent when transferred to the substrate, and has no fluidity when transferred to the substrate, so that the thickness uniformity of the organic electronics layer after transfer can be increased. It is said that.

JP 2001-93668 A JP 2001-155858 A Japanese Patent No. 3911775 JP 2003-17261 A

Conventionally, when a material for forming an organic semiconductor layer of an organic transistor or a material for forming an organic light emitting medium layer of an organic EL is printed on a substrate by a pattern printing method, the organic light emitting material is water or an organic solvent (necessary Depending on the case, ink dispersed or dissolved in a binder resin) is used.
However, in general, an organic light-emitting material that can be converted to an ink has a maximum solid content ratio of about 5% by mass with respect to the solvent even when the solubility in the solvent is high. It is easy to precipitate as. For this reason, it is difficult to increase the viscosity of the ink. The organic semiconductor layer of the organic transistor is made of an organic EL organic light emitting medium, although many of the materials having the same pi-conjugated aromatic structure as the organic EL organic light emitting medium layer are used. Since the interaction between materials is stronger than the material forming the layer, the solubility in a solvent is generally low.

  On the other hand, when the material for forming the organic electronics layer is formed into a pattern and driven as an element, it is said that the durability of the element is preferably higher in the purity of the film to be formed. For this reason, viscosity modifiers such as thickeners are difficult to add because they remain in the film to be deposited and cause a decrease in purity. For this reason, it is difficult to increase the viscosity of the ink of the material forming the organic electronics layer to several tens mPa · s or more. In particular, it is impossible to increase the viscosity of a material having a molecular weight of 100,000 or less.

By the way, it is known that the ink used for various pattern printing methods, such as an offset printing method, a relief printing method, and an intaglio printing method, has an optimal viscosity.
However, in the manufacture of organic electronics devices, as described above, the processes that can be used are limited due to the restriction that the ink of the material forming the organic electronics layer has a low viscosity.
The wet coating method described above as a method used in the process can be generally used even if the ink has a low viscosity.
On the other hand, in the above-described pattern printing methods (offset printing method, letterpress printing method, etc.), the film thickness of the organic electronics layer tends to be non-uniform, so the ink of the material forming the organic electronics layer forms the pattern with good reproducibility. It can be said that it has a difficult viscosity region.

In addition, as represented by the pixel structure of a display, ink is applied to a patterned substrate having a partition formed of resin or the like on the substrate and an opening surrounded by the partition by a wet coating method or an inkjet printing method. The method of flowing into the opening is performed as an actual process.
In this case, when low viscosity ink is allowed to flow into the opening, the ink adheres to the partition wall, and a meniscus structure having a curvature due to surface tension is formed in the vicinity of the partition wall. Therefore, the phenomenon that the end of the organic electronics layer near the partition wall becomes thick cannot be avoided.

  In addition, when plasma treatment using a fluorinated carbon gas is performed on the partition wall and ink is driven into the opening by an ink jet printing method, the affinity between the partition wall surface and the ink is low. By biasing toward the end, the organic electronics layer end on the peripheral side of the opening tends to be thin. In this case, since it is difficult to control the wettability of the partition walls with respect to the ink and the drying conditions, it is difficult to improve the film thickness uniformity of the organic electronics layer.

  In addition, when pattern printing of a certain large area is performed to produce a display screen or the like, there is a difference in drying speed because the solvent atmosphere such as vapor pressure is different between the pattern periphery (display periphery) side and the center side. Arise. Therefore, the meniscus structure is unevenly formed among a plurality of elements, and the film thickness of the organic electronics layer is different, for example, the amount of ink flowing in is different, resulting in slightly different performance for each element. . In particular, this influence increases as the definition of the pattern to be formed becomes finer.

On the other hand, in each pattern printing method, in order to make the drying speed uniform, the drying speed is moderated by using a high boiling point solvent, or printing is performed intentionally on unnecessary portions on the substrate, There has been proposed a method for eliminating the difference in vapor pressure from a necessary location.
However, in these methods, the throughput is reduced in order to dry the solvent having a high boiling point, the performance of the material forming the organic electronics layer is deteriorated due to high temperature drying, or printing is performed in an unnecessary place, so that the organic There are problems such as an increase in the consumption of materials forming the electronics layer and an increase in cost.

  In the invention of Patent Document 4, since the elastic silicone blanket is easily deformed, the printing pressure and the swelling due to the solvent contained in the material forming the organic electronics layer cannot be avoided, and the position of the pattern to be formed There is a problem that it is very difficult to obtain accuracy.

This invention is made | formed in view of the said situation, and makes the subject the manufacturing method of an organic electronics device using the new printing method which solves the said problem, and an organic electronics device.
Specifically, in printing using low-viscosity ink, an organic electronics device manufacturing method and an organic electronics device having excellent reproducibility of high-definition pattern printing and high film thickness uniformity of the organic electronics layer The issue is to provide. In particular, it is an object of the present invention to provide an organic electronic device manufacturing method and an organic electronic device capable of forming an organic electronic layer with a uniform thickness up to the end thereof.

In order to solve the above problems, the present invention employs the following configuration.
That is, the method for manufacturing an organic electronics device according to one embodiment of the present invention includes a liquid repellent portion that exhibits liquid repellency with respect to a solvent contained in the ink forming the organic electronics layer, and a lyophilic property with respect to the solvent. A step of producing a patterned substrate on which a pattern having a lyophilic portion is formed, a step of applying the ink on a blanket to form an organic electronics layer, and the organic electronics layer on the patterned substrate. And a step of transferring the organic electronics layer to the lyophilic portion in contact with each other.

The organic electronic device manufacturing method according to an aspect of the present invention is characterized in that the liquid repellent portion is formed by plasma treatment with carbon tetrafluoride gas.
The organic electronic device manufacturing method according to an aspect of the present invention is characterized in that the liquid repellent portion is formed by patterning with a resist containing a fluororesin.

  An organic electronic device according to an aspect of the present invention is manufactured by the method for manufacturing an organic electronic device of the present invention.

  According to the present invention, in printing using low-viscosity ink, the reproducibility of high-definition pattern printing is excellent, and the film thickness uniformity of the organic electronics layer is high. A method for producing an organic electronic device capable of forming a film with a sufficient thickness and an organic electronic device can be provided.

FIG. 1A is a plan view and FIG. 1B is a cross-sectional view taken along line AA in FIG. 1A. It is sectional drawing for demonstrating one embodiment of the method of forming an organic electronics layer (organic EL layer) on a blanket. 3A to 3C are cross-sectional views for explaining an embodiment of a method for transferring an organic electronics layer (organic EL layer) formed on a blanket to a substrate with a pattern. It is sectional drawing to which a part of FIG.3 (b) was expanded. FIG. 5A is a cross-sectional view showing the film shape of an organic EL layer in the vicinity of an opening, FIG. 5A is formed by the present invention, FIG. 5B is formed by an inkjet method, and FIG. 5C is formed by a spin coating method. It is sectional drawing which shows the film | membrane shape of an organic electroluminescent layer. It is a top view of the pattern which consists of a partition and the opening part enclosed by this partition obtained by the photolithographic method in a present Example.

<Method for manufacturing organic electronics device>
An organic electronics device manufacturing method according to an embodiment of the present invention includes a liquid repellent portion that exhibits liquid repellency with respect to a solvent contained in ink forming an organic electronics layer, and a liquid lyophobic property with respect to the solvent. A step of manufacturing a patterned substrate on which a pattern having a lyophilic part is formed (hereinafter referred to as “patterned substrate manufacturing step”), and a step of forming an organic electronics layer by applying the ink on a blanket ( Hereinafter referred to as “organic electronics layer forming step”) and a step of bringing the organic electronics layer into contact with the patterned substrate and transferring the organic electronics layer to the lyophilic portion (hereinafter referred to as “transfer step”). And have.
The present embodiment is a method of manufacturing an organic electronic device such as an organic transistor such as an organic thin film transistor (TFT), organic electroluminescence (organic EL), or organic EL display.

(ink)
The ink contains a material constituting the organic electronics layer and a solvent.
Examples of the material constituting the organic electronics layer include the followings in the case of organic transistors and organic ELs.
In the case of an organic transistor, pentacene, naphthacene, thiophene oligomer, perylene, α-sexiphenyl or a derivative thereof, naphthalene, anthracene, rubrene or a derivative thereof, coronene or a derivative thereof, metal-containing / non-containing phthalocyanine or a derivative thereof, etc. Low molecular semiconductors: High molecular semiconductors such as polyalkylthiophene, polyalkylfluorene or derivatives thereof based on thiophene or fluorene.
In the case of the organic EL, any of a low molecular material and a high molecular material can be used as the light emitting material. The polymer material is preferable because it can be dissolved or stably dispersed in a solvent and has good ink stability. In recent years, there are also low molecular weight materials that can be applied as inks. Conventionally, the formation of a low molecular material by vacuum deposition has been the mainstream, but the use of a polymer material has the advantage that film formation under atmospheric pressure is possible and the equipment cost is low. Specific examples of the luminescent material include low molecular fluorescent dyes dissolved in polymers such as polystyrene, polymethyl methacrylate, and polyvinyl carbazole; polyphenylene vinylene derivatives (PPV), polyalkylfluorene derivatives (PAF), and the like. Examples thereof include molecular phosphors. Among these, a phosphorescent polymer material is preferable because of high luminous efficiency.
Examples of the solvent include water, toluene, xylene, ethylbenzene, anisole, mesitylene, methoxytoluene, amylbenzene, tetralin, dimethyltetralin, dimethoxybenzene, and phenylcyclohexane.
The content of the material constituting the organic electronics layer in the ink is preferably 0.3 to 2.5% by mass with respect to the total mass of the ink because the solubility or dispersibility in the solvent is good. More preferably, the content is 0.5 to 1.5% by mass.

  Hereinafter, an organic EL display manufacturing method will be described as an embodiment of the organic electronic device manufacturing method of the present invention.

[Pattern manufacturing process with pattern]
In this step, a pattern having a liquid-repellent part that exhibits liquid repellency with respect to the solvent contained in the ink that forms the organic electronics layer and a lyophilic part that exhibits lyophilicity with respect to the solvent is formed. A substrate with a patterned pattern is produced.
1A and 1B show an embodiment of a substrate with a pattern, FIG. 1A is a plan view, and FIG. 1B is a cross-sectional view taken along line AA in FIG.
The substrate 10 with a pattern of this embodiment includes a substrate 13, a transparent electrode 14 laminated on one surface of the substrate 13, and a partition wall 12 formed on the transparent electrode 14. On the substrate with pattern 10, the partition wall 12 and the opening 11 surrounded by the partition wall 12 are respectively surface-treated to form a lattice pattern including a liquid repellent portion 12 a and a lyophilic portion 11 a. The lyophilic portion 11a becomes a light emitting pixel portion.

The patterned substrate 10 can be manufactured as follows, for example.
A transparent electrode 14 is laminated on the substrate 13 by depositing a transparent electrode material by vacuum deposition or patterning.
Examples of the substrate 13 include a glass substrate and a flexible film substrate. The thickness of the substrate 13 is preferably about 0.02 to 1 mm (millimeter).
For the transparent electrode 14, a metal oxide film (ITO) or the like is used when light is extracted from the substrate 13 side, and a highly reflective metal electrode or the like is used when light is extracted from the side opposite to the substrate 13.
As the substrate 13 on which the transparent electrode 14 is stacked, a substrate having a wiring pattern for input / output of an electric signal that is passively driven can be used.

Next, patterning is performed on the transparent electrode 14 so as to draw a lattice pattern using a resist. Thereby, the partition 12 and the opening part 11 enclosed by the partition 12 are formed in a grid | lattice form.
As the resist, a commonly used polymer resist such as polyimide, novolak, and acrylic can be used, and may be a positive resist or a negative resist.
The height of the partition wall 12 is preferably 5 μm (micrometer) or less.

  Thereafter, the surface of the opening 11 and the partition wall 12 is subjected to surface treatment, whereby the surface of the opening 11 becomes a lyophilic portion 11a that is lyophilic with respect to the solvent contained in the ink, and the surface of the partition wall 12 is in contact with the solvent. On the other hand, the substrate 10 with a pattern to be the liquid repellent portion 12a exhibiting liquid repellency is produced.

In the present invention, “showing lyophilicity with respect to a solvent” is included in the ink, which is measured by a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., product name: Face Contact Angle Meter model CA-D). It means that the contact angle with respect to the solvent is 20 ° (degrees) or less.
Further, “showing liquid repellency with respect to the solvent” means that the contact angle with respect to the solvent contained in the ink is 50 ° or more as measured by the contact angle measuring device. When the solvent contained in the ink is an aromatic compound such as toluene, xylene, and anisole, the uniformity of the thickness of the transferred organic electronics layer is increased. Therefore, the contact angle of the liquid repellent part 12a with respect to the solvent is set to 70. It is preferable that the angle be at least.

  Examples of the method for forming the lyophilic portion 11a by surface-treating the opening 11 include oxygen plasma treatment and ultraviolet / ozone cleaning.

As a method of forming the liquid repellent portion 12a by surface-treating the partition wall 12, there is a method of applying a liquid repellent material to the surface of the partition wall 12 by a general coating method such as spray coating, curtain coating, die coating, dip coating or the like. Can be mentioned.
Among these, a method of applying a liquid repellent material to the surface of the partition wall 12 by spray coating or dip coating is preferable because it is a simple method. However, when using these methods, in order to prevent the liquid repellent material from adhering to the opening 11 or the lyophilic portion 11a, the resist is applied to the opening 11 or the lyophilic portion 11a. After forming the liquid repellent material layer on the resist film surface, the resist film is preferably removed by development.
Examples of the liquid repellent material include those obtained by dissolving or dispersing a fluororesin and a silicone-based material (silicone resin or the like) in a solvent.

  Moreover, as a method of forming the liquid-repellent portion 12a by surface-treating the partition walls 12, a method of performing plasma treatment with carbon tetrafluoride gas is preferable because it is a simple method. When carbon tetrafluoride gas is used, only the resin portion can be fluorinated and liquid repellency can be imparted to the surface of the partition wall 12.

As a method of forming the lyophilic part 11a and the liquid repellent part 12a, since it is simpler, after forming the openings 11 and the barrier ribs 12 in a lattice pattern on the transparent electrode 14, oxygen plasma treatment, or A method of imparting lyophilicity to the opening 11 by performing at least one of ultraviolet / ozone cleaning and then imparting liquid repellency to the surface of the partition wall 12 by plasma treatment with carbon tetrafluoride gas is preferable.
In addition, after imparting liquid repellency to the surface of the partition wall 12, lyophilicity can be imparted to the opening 11. The effect of imparting liquid repellency to the surface of the partition wall 12 may be reduced due to the influence of oxygen plasma treatment or ultraviolet / ozone cleaning. In that case, the liquid repellency is improved by heat-treating the surface of the partition wall 12.

[Organic electronics layer formation process]
In this step, the ink is applied on a blanket to form an organic electronics layer.
FIG. 2 is a cross-sectional view for explaining an embodiment of a method for forming an organic electronics layer (organic EL layer) on a blanket.
In the method of this embodiment, a very simple circular pressure type printing machine 20 is used. The printing machine 20 includes a blanket cylinder 21 that rotates about a rotation axis, a blanket 22 that is fixed to a part of the surface of the blanket cylinder 21, and an ink discharge port 23 that supplies ink to the blanket 22.
As the blanket cylinder 21, a metal or resin hard roll, a hard roll having appropriate elasticity, or the like is used.
The blanket 22 is required to have solvent resistance to a solvent (particularly aromatic compounds such as toluene, xylene, anisole, etc.) contained in the ink.
The blanket 22 is made of nitrile rubber, silicone rubber, isoprene rubber, styrene butadiene rubber, butadiene rubber, chloroprene rubber, butyl rubber, acrylonitrile rubber, ethylene propylene rubber, urethane rubber, etc .; polyethylene, polystyrene, polybutadiene, polyvinyl chloride Synthetic resins such as polyvinylidene chloride, polyvinyl acetate, polyamide, polyethersulfone, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, and polyvinyl alcohol, or a copolymer having two or more repeating units constituting these synthetic resins. Polymers: Natural polymers such as cellulose, fluororesins, etc. can be used. Of these, rubber and fluororesin are preferred because of their good releasability during transfer to the patterned substrate 10. Of the rubbers, silicone rubber is particularly preferable.

According to the present embodiment, ink is supplied from the ink discharge port 23 onto the blanket 22 while the blanket cylinder 21 rotates in the direction of the arrow about the rotation axis. The ink supplied to the entire surface of the blanket 22 is dried to such an extent that it does not flow on the blanket 22, and an organic EL layer 30 covering the entire surface of the blanket 22 is formed with a uniform thickness.
The drying conditions may be appropriately determined depending on the ink composition, transfer conditions (printing pressure, printing speed, humidity, etc.) and the like. For example, it is preferable to set the drying temperature and drying time shown below according to the type of solvent contained in the ink. However, the drying temperature and drying time in each solvent shown below are controlled by the type of material constituting the organic EL layer 30 included in the ink, the case where a mixed solvent is used as the solvent, and the like.
(Group A)
Drying temperature: toluene 110 ° C, xylene 138 ° C, ethylbenzene 136 ° C
Drying time: About 5 to 10 seconds at each of the above drying temperatures (Group B)
Drying temperature: Anisole 154 ° C, mesitylene 165 ° C, methoxytoluene 174 ° C
Drying time: About 10 to 30 seconds at each of the above drying temperatures (Group C)
Drying temperature: amylbenzene 205 ° C, tetralin 207 ° C, dimethoxybenzene 207 ° C, phenylcyclohexane 240 ° C
Drying time: 30 seconds to several minutes at each of the above drying temperatures

  The amount of ink supplied onto the blanket 22 may be appropriately determined according to the set film thickness of the organic EL layer 30.

[Transfer process]
In this step, the organic electronics layer formed on the blanket is brought into contact with the patterned substrate, and the organic electronics layer is transferred to the lyophilic portion.
3A to 3C are cross-sectional views for explaining an embodiment of a method for transferring an organic electronics layer (organic EL layer) formed on a blanket to a substrate with a pattern.

In the present embodiment, the patterned substrate 10 and the printing machine 20 placed on the movable surface plate 40 are arranged at predetermined positions (FIG. 3A).
The blanket cylinder 21 rotates in the direction of the arrow about the rotation axis at a speed corresponding to the set printing speed or the like, and the patterned substrate 10 advances in the direction of the arrow.
At that time, the organic EL layer 30 contacts the liquid repellent portion 12a and the lyophilic portion 11a (FIG. 3B).
FIG. 4 is an enlarged cross-sectional view of a part of FIG.
When the organic EL layer 30 comes into contact with the liquid repellent part 12a and the lyophilic part 11a, the organic EL layer 30 is not transferred to the liquid repellent part 12a but transferred to the lyophilic part 11a.
In this way, the organic EL layer 30 formed on the blanket 22 is transferred only to the lyophilic portion 11a of the patterned substrate 10 (FIG. 3C).

Next, the solvent remaining in the organic EL layer 30 after the transfer is removed by drying or the like.
Next, a cathode is formed by laminating a calcium layer, an aluminum layer, or the like on the organic EL layer 30 by vacuum deposition or patterning.
Then, an organic EL display is manufactured by sealing or the like.

(Function and effect)
In the manufacturing method of the organic electronics device of this embodiment shown in FIGS. 1 to 4, the pattern position is always constant because the pattern is formed on the substrate 13 side. Therefore, it is only necessary to form the organic EL layer 30 on the entire surface of the blanket 22 on the blanket 22 side, and when transferring to the substrate 13 side, there is no need to worry about the transfer position of the organic EL layer 30 and high definition. Pattern printing can be performed with good reproducibility. In addition, an organic EL element can be produced advantageously in terms of yield and throughput.
Moreover, in the manufacturing method of the organic electronics device of this embodiment, the organic EL layer 30 is once formed on the blanket 22. Thereby, it is possible to form a film stably even with a low viscosity ink. Furthermore, since the organic EL layer 30 formed with a predetermined film thickness on the blanket 22 is transferred to the substrate 13 side, the film thickness uniformity of the organic EL layer 30 is high. In addition, the organic EL layer 30 is transferred only to the lyophilic part 11a by using the patterned substrate 10 on which the pattern having the lyophobic part 12a and the lyophilic part 11a is formed. The organic EL layer 30 can be formed with a uniform thickness up to the periphery of the portion 11 (the end of the organic EL layer 30). As a result, the organic EL element emits uniform light over the entire pixel surface.

FIG. 5 is a cross-sectional view showing the film shape of the organic EL layer around the opening.
5A shows the film shape of the organic EL layer formed by the present invention, FIG. 5B shows the ink jet method, and FIG. 5C shows the spin coating method.
In FIG. 5A, the organic EL layer 30 having a uniform thickness is formed up to the periphery of the opening (interface with the partition wall 12). This is because the organic EL layer 30 once formed to a predetermined thickness on the blanket 22 is transferred to the substrate 13 side, and the organic EL layer 30 on the blanket 22 does not flow on the blanket 22. This is because it is dried and contains a moderate amount of solvent, so that it can be easily peeled off from the blanket 22 due to its affinity with the lyophilic portion 11a.
In FIG. 5B, the periphery of the opening is thinned. This is because the ink surface tends to be biased toward the center of the opening due to the low affinity between the liquid repellent portion 12a and the ink.
In FIG. 5C, the periphery of the opening is thickened. This is because when low-viscosity ink flows into the opening, the ink adheres to the surface of the partition 12 on the opening side, and a meniscus structure having a curvature due to surface tension is formed.

In the production method of the present invention, all organic electronic materials can be used.
In particular, the manufacturing method of this embodiment in which the organic EL layer 30 is transferred to the lyophilic portion 11a is suitable for stacking organic materials because the organic EL layer 30 itself is a lyophilic layer. Yes.

The method for producing an organic electronic device of the present invention is not limited to the embodiment shown in FIG. 1, and a patterned substrate on which a pattern structure other than a lattice shape is formed may be used.
In the embodiment shown in FIG. 1, the partition wall 12 may be a lyophilic portion and the opening 11 may be a liquid repellent portion.
Further, in the patterned substrate manufacturing process, a pattern printing method using a resin or the like is used as a method for forming the partition wall 12 and the opening 11 surrounded by the partition wall 12 on the transparent electrode 14 (forming a pattern structure). You can also.
In addition, as a method for forming the liquid repellent portion, a method of forming a partition wall by patterning using a material obtained by adding a fluororesin or a silicone-based material (silicone resin or the like) to the resist is also preferable. Among these, a method of performing patterning with a resist containing a fluororesin is particularly preferable. In this case, since the partition formed is not only the surface but also the entire partition exhibits liquid repellency with respect to the solvent contained in the ink, it is easy to obtain a printed matter with few pattern defects. Examples of the fluororesin include a fluoroelastomer, polytetrafluoroethylene, polyvinylidene fluoride, poly (vinylidene fluoride), or a copolymer having two or more repeating units constituting these polymers.
Further, a substrate with a pattern in which a pattern having a liquid repellent part and a lyophilic part, which is not provided with a partition wall, can be used. In this case, the organic electronics layer can be transferred satisfactorily by controlling the dry state of the organic electronics layer formed on the blanket.
Moreover, you may have another process before and after each process mentioned above. Examples of the other steps include a hole transport layer forming step provided between the patterned substrate manufacturing step and the organic electronics layer forming step.

Another embodiment of the method for producing an organic electronic device of the present invention includes a method for producing an organic thin film transistor (TFT) as follows.
Forming a gate electrode on a substrate, laminating a gate insulating film on the entire surface, and using the ink containing the material constituting the organic semiconductor layer and a solvent on the gate insulating film, the above-described patterned substrate manufacturing process A TFT is manufactured by forming an organic semiconductor layer in the same manner as the organic electronics layer forming step and the transfer step, and then forming a source electrode and a drain electrode at a predetermined channel interval.

  When it is not necessary to transfer the organic electronics layer to the substrate side in a pattern, a support (laminated body of a substrate and a transparent electrode) is used in which the entire surface on which the organic electronics layer is transferred is a lyophilic portion. Thus, the entire surface of the organic electronics layer formed on the blanket can be transferred to the lyophilic portion. By this method, an organic electronics layer having a uniform film thickness can be formed up to the periphery of the support.

<Organic electronics devices>
An organic electronic device according to an embodiment of the present invention is manufactured by the method for manufacturing an organic electronic device according to the embodiment of the present invention.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
-Preparation of Organic Light-Emitting Layer Ink (X) As a light-emitting material constituting the organic EL layer, a polymeric fluorescent substance composed of a poly (paraphenylene vinylene) derivative represented by the following chemical formula (1) was used. N in the formula represents the number of repetitions.
As the solvent, a 1: 1 mixed solvent of xylene and anisole was used.
By dissolving the polymeric fluorescent substance in the mixed solvent, an organic light emitting layer ink (X) having a polymeric fluorescent substance concentration of 0.6% by mass was prepared.

-Printing machine The printing machine used the substantially same embodiment as the printing machine 20 shown in FIG.
Specifically, as a printing machine, a roll part (a blanket cylinder), a printing blanket fixed to a part of the surface of the roll part, and an air extrusion for supplying the organic light emitting layer ink (X) to the printing blanket A printing test machine equipped with a system type slit die (slit width 30 μm) was used.
The printing blanket is a two-part silicone rubber (made by Momentive Performance Materials Japan G.K.) molded into a length of 150 mm, a width of 100 mm, and a thickness of 5 mm. Fixed with.

Example 1
[Pattern manufacturing process with pattern]
A positive electrode is formed on the ITO film side of a transparent electrode base material (manufactured by Geomat Co., Ltd.) in which an ITO film having a surface resistivity of 15Ω is formed in a circuit pattern on a 100 mm square, 0.7 mm thick glass substrate. Photosensitive polyimide DL1000 (manufactured by Toray Industries, Inc.) was formed into a pattern with a thickness of 3 μm by photolithography.

FIG. 6 is a plan view of a pattern made of a partition and an opening surrounded by the partition, obtained by photolithography in this example.
The height of the partition wall 12 was 3 μm, and the size of one opening 11 was 108 μm in length and 76 μm in width. This size of openings 11 is arranged in a pseudo manner in which 50 vertical and 150 horizontal openings 11 are arranged at a vertical pitch of 318 μm (vertical arrow in the plan view) and a horizontal pitch of 106 μm (horizontal arrow in the plan view). A passive display structure was fabricated.

Next, lyophilicity was imparted by treating the ITO surface with oxygen plasma for 3 minutes. Thereafter, plasma treatment was performed with carbon tetrafluoride gas to impart liquid repellency to the partition wall surface.
At this time, the contact angle of the partition wall surface was 86 ° with respect to xylene. The contact angle of the surface of the opening was 11 ° as a contact angle with respect to xylene. The contact angle was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., product name: Face Contact Angle Meter model CA-D).
Thus, a patterned substrate on which a pattern having a liquid repellent portion and a lyophilic portion was formed was produced (the obtained patterned substrate is substantially the same as the embodiment shown in FIG. 1).

[Organic electronics layer formation process]
The organic light emitting layer ink (X) was supplied from the slit die to the entire surface of the printing blanket while rotating the roll portion around the rotation axis. Next, the organic light emitting layer ink (X) supplied to the entire surface of the printing blanket is dried at 25 ° C. for 15 seconds until it does not flow on the printing blanket, and the organic EL layer covering the entire surface of the printing blanket is uniformly formed. The film was formed with a thickness (53 nm).

[Transfer process]
Transfer was carried out according to an embodiment substantially the same as the embodiment shown in FIGS. Specifically, a substrate with a pattern placed on a moving surface plate and a printing press having an organic EL layer formed on a printing blanket are placed at predetermined positions, and the drying process in the previous step has elapsed for 15 seconds. From this point, the organic EL layer formed on the printing blanket was brought into contact with the substrate with pattern and transferred. As a result, the organic EL layer was transferred only to the lyophilic portion of the patterned substrate.

Next, the substrate with a pattern to which the organic EL layer was transferred was dried in a vacuum oven at 100 ° C. for 2 hours to remove the solvent remaining in the organic EL layer after transfer.
Subsequently, the substrate with a pattern was put into a vacuum evaporation machine (manufactured by ULVAC), and a cathode layer was formed by sequentially laminating a calcium layer 7 nm and an aluminum layer 80 nm to obtain an organic EL display composed of a plurality of organic EL elements.

(Example 2)
In the same manner as in Example 1, a patterned substrate on which a pattern having a liquid repellent part and a lyophilic part was formed was produced.

Next, a poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (PEDOT / PSS) represented by the following chemical formula (2) is formed into a film with a film thickness of 50 nm on the obtained patterned substrate by an inkjet method. Thus, a hole transport layer was formed.
Subsequently, this PEDOT / PSS thin film was dried at 180 ° C. for 1 hour under reduced pressure.

  Thereafter, in the same manner as in Example 1, an [organic electronics layer forming step], a [transfer step], drying, and formation of a cathode were performed to obtain an organic EL display composed of a plurality of organic EL elements.

(Comparative Example 1)
An organic light emitting layer ink (Y) having a polymer phosphor concentration of 1.5 mass% is prepared by dissolving a polymer phosphor composed of a poly (paraphenylene vinylene) derivative represented by the chemical formula (1) in cyclohexylbenzene. ) Was prepared.
In Example 2, after forming the hole transport layer by the inkjet method, the organic light emitting layer ink (Y) was also formed by the inkjet method to form the organic EL layer.
Next, it was dried at a hot plate at 100 ° C. for 10 minutes and then dried in a vacuum oven at 100 ° C. for 2 hours to remove the solvent remaining in the organic EL layer.
Next, a cathode was formed in the same manner as in Example 1 to obtain an organic EL display composed of a plurality of organic EL elements.

<Evaluation results>
In Example 1, strict alignment was not required during transfer, and the reproducibility of high-definition pattern printing was excellent.
When a voltage was applied to the organic EL display manufactured by the manufacturing method of Example 1 through the ITO film to check the light emission state, the film thickness distribution in the pixel was 48 nm ± 8 nm. From this result, it was confirmed that the film thickness was high and the thickness was uniform up to the end of the organic EL layer.
Further, uniform light emission was exhibited over the entire pixel surface. The luminance of light emission was 30 cd / m ² at 10V.

In Example 2, strict alignment was not required during transfer, and the reproducibility of high-definition pattern printing was excellent.
When a voltage was applied to the organic EL display manufactured by the manufacturing method of Example 2 through the ITO film to check the light emission state, the film thickness distribution in the pixel was 45 nm ± 9 nm. From this result, it was confirmed that the film thickness was high and the thickness was uniform up to the end of the organic EL layer. In addition, even when the organic material (PEDOT / PSS) was formed in the pixel as a lyophilic layer, it was confirmed that the printability was not affected and the organic EL layer could be formed with a uniform film thickness.
Further, uniform light emission was exhibited over the entire pixel surface. In Example 2, since a hole transport layer was introduced, the luminance was improved as compared with Example 1, and the luminance of light emission was 150 cd / m ² at 10V.

In Comparative Example 1, since the inkjet method was used, coating unevenness occurred and the reproducibility of high-definition pattern printing was poor.
When a voltage was applied to the organic EL display manufactured by the manufacturing method of Comparative Example 1 through the ITO film to confirm the light emission state, the film thickness distribution in the pixel was 50 nm ± 22 nm, and the center of the pixel Is thick, the film thickness is about 70 nm, the film thickness around the pixel is 30 nm or less, and has a convex shape.
Further, the periphery of the pixel where current easily flows emitted light strongly, resulting in uneven light emission. Furthermore, since the peripheral portion of the pixel is thin, many pixels that cause a short circuit and do not emit light are also seen.

DESCRIPTION OF SYMBOLS 10 Patterned substrate 11 Opening part 11a Lipophilic part 12 Partition 12a Liquid repellent part 13 Substrate 14 Transparent electrode 20 Printing machine 21 Blanket cylinder 22 Blanket 23 Ink ejection port 30 Organic EL layer 40 Moving surface plate

Claims (4)

A substrate with a pattern on which a pattern having a liquid repellent part exhibiting liquid repellency with respect to a solvent contained in ink forming the organic electronics layer and a lyophilic part exhibiting lyophilic property with respect to the solvent is formed A step of producing
Applying the ink on a blanket to form an organic electronics layer;
And a step of bringing the organic electronics layer into contact with the substrate with pattern and transferring the organic electronics layer to the lyophilic portion.   2. The method of manufacturing an organic electronic device according to claim 1, wherein the liquid repellent part is formed by plasma treatment with carbon tetrafluoride gas.   3. The method of manufacturing an organic electronic device according to claim 1, wherein the liquid repellent part is formed by patterning with a resist containing a fluororesin.   An organic electronic device manufactured by the method for manufacturing an organic electronic device according to any one of claims 1 to 3.

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