JP2015159083A - Manufacturing method of organic EL device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing an organic EL device that can surely form a protection film at a desired position and suppress a protection film formed on a mask from being exfoliated from the mask and become a foreign matter.SOLUTION: A mask 2 which is opened at a formation scheduled area for a protection film 4 is disposed on a substrate 1 having an organic EL element, and then SAM 3 is formed on a portion exposed from the mask 2 on the surface of the substrate 1 and on the surface of the mask 2. Thereafter, the protection film 4 is formed on the surface of the substrate 1 having SAM 3 formed thereon and the surface of the mask 2 by using gas. As a substrate 1, a material is used which is brought into close contact with the mask 2, chemically adsorbed by SAM 3 and also is not chemically adsorbed by the material of the protection film 4. A material which is chemically adsorbed by SAM 3 while brought into close contact with the substrate 1 is used as the mask 2, and a material which is chemically adsorbed by SAM 3 and is not chemically adsorbed by the substrate 1 is used as the protection film 4.

Description

  The present invention relates to a method for manufacturing an organic EL device in which a protective film is formed on a surface of an organic EL element by film formation using a gas.

  Conventionally, in an organic EL device in which a plurality of organic EL elements are arranged on a substrate to form a panel, a protective film is formed so as to cover the organic EL elements. Such a protective film is formed only at a desired position on the base material, and is not formed at a place where the wiring pattern is to be exposed, for example.

  As a method for forming such a protective film only at a desired position, there are a method using a mask and a method using a SAM process (self-assembled monolayer).

  In the method using the mask, the protective film is formed in a state where the mask is arranged so as to cover the position where the protective film is not to be formed, so that the protective film is formed only at a desired position exposed from the mask. I am doing so.

  In the method using the SAM treatment, a SAM is formed on the surface of the base material on which the organic EL element or the like is formed by the SAM treatment, and then a protective film forming gas is sprayed. Thus, a protective film is formed in a portion where the SAM is not formed. In other words, by forming the SAM, the surface of the protective film forming gas molecules is difficult to be adsorbed, and the protective film forming gas molecules are adsorbed only at a desired position where the SAM is not formed. It is made to form (refer patent document 1).

Special Table 2013-520028

  However, in the method using a mask, when a protective film is formed using a gas such as an ALD (Atomic Layer Deposition) method, if the mask is not in close contact with the base material, Gas goes around from the gap. For this reason, there exists a problem that a protective film will be formed to the position which does not want to form into a film. In particular, when a substrate is heated when a protective film is formed using a gas, the mask and the substrate may not be able to secure adhesion due to warpage, undulation, or distortion of the mask. Is likely to occur. Furthermore, since the protective film formed also on the mask peels off from the mask and becomes a foreign substance, which causes deterioration of the characteristics of the organic EL device, there is a problem that it is difficult to reuse the mask.

  In addition, in the method using SAM treatment, if particles or the like are present on the surface of the SAM such as a base material, a region where the SAM is not partially formed is formed due to the influence, and a protective film is also formed on the region. There is a problem of being done. In particular, when the area where the SAM processing is performed is a large area, it is difficult to form the SAM uniformly, and such a problem is likely to occur.

  In view of the above points, the present invention can accurately form a protective film at a desired position, and can further prevent the protective film formed on the mask from peeling off from the mask to become a foreign substance. An object of the present invention is to provide a method for manufacturing an organic EL device.

  In order to achieve the above object, in the invention according to claims 1 to 5, after the formation process of the self-assembled monolayer (3) is performed on the base material (1) provided with the organic EL element, A method of manufacturing an organic EL device that forms a protective film (4) at a desired position on the surface of a substrate using a gas, wherein the material of the protective film is not chemisorbed and the material of the self-assembled monolayer is chemical A step of preparing a base material composed of a material that is adsorbed and to which a mask adheres, and a desired position on the surface of the base material opens on the surface of the base material, and the self-assembled monolayer material is chemisorbed And a self-assembled monolayer that promotes chemisorption of the material forming the protective film on the surface of the substrate at a desired position on the surface of the substrate and the surface of the mask. The process of forming and not chemically adsorbing to the substrate, Using a gas containing a protective film made of a material that is chemically adsorbed to the self-assembled monolayer, the self-assembled monolayer formed on the surface of the mask and the desired position on the surface of the substrate is used. And a step of forming a protective film on the surface.

  In such a manufacturing method, even when a gap is formed between the base material and the mask when the protective film is formed and the gas wraps into the gap, the protective film is not formed on the surface other than the surface of the SAM. You can A protective film is also formed on the mask. Since SAM is formed on the surface of the mask, SAM is chemisorbed on the mask, and the protective film is chemisorbed on the SAM. It is in the state that was done. For this reason, it can suppress that a protective film becomes difficult to peel from a mask and becomes a foreign material. Therefore, since the protective film formed on the mask is peeled off and becomes a foreign substance, it does not cause deterioration of the characteristics of the organic EL device, and the mask can be used repeatedly.

  Therefore, a method of manufacturing an organic EL device capable of accurately forming a protective film at a desired position and further suppressing the protective film formed on the mask from peeling off from the mask to become a foreign substance. Is possible.

  In addition, the code | symbol in the bracket | parenthesis of each said means shows an example of a corresponding relationship with the specific means as described in embodiment mentioned later.

It is sectional drawing which showed the manufacturing process of the organic electroluminescent apparatus concerning 1st Embodiment of this invention. It is the figure which showed the mode of the base material 1 terminated with hydrogen. 1 is a view showing a state when a silane coupling agent having an amino group is adsorbed on the surface of a base material 1. FIG.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following embodiments, parts that are the same or equivalent to each other will be described with the same reference numerals.

(First embodiment)
The manufacturing method of the organic EL device according to the first embodiment of the present invention will be described with reference to the respective manufacturing steps shown in FIGS.

[Step shown in FIG. 1 (a)]
First, a base material 1 is prepared, and a mask 2 is set on the base material 1. Although not shown, the substrate 1 is provided with a plurality of organic EL elements arranged side by side and a wiring pattern for driving each organic EL element.

  At this time, as the material of the base material 1, the protective film 4 (FIG. 1 (FIG. 1)) is adhered to the mask 2 and is chemically adsorbed by a material used in the SAM treatment described later. The material of (c) is not chemically adsorbed. For example, a glass substrate, a silicon substrate, a polyimide substrate or the like is used as the base material 1. As the mask 2, a hard mask composed of a material that is chemically adsorbed by a material used in the SAM process while being in close contact with the base material 1 is used. For example, glass, SUS, resin, or the like is used as the material for the mask 2. The material of the mask 2 can be selected as appropriate, but it is preferable to use the material properly depending on the film formation temperature in consideration of the deformation of the mask 2.

  As shown in FIG. 2, the surface of the base material 1 prepared in this way has a structure in which hydroxyl groups (OH groups) are chemically adsorbed by moisture contained in the atmosphere and terminated with hydroxyl groups. In addition to the layers constituting the organic EL element, for example, the lower electrode layer, the organic EL layer, the upper electrode layer, and the like, the substrate 1 is formed with a wiring pattern, etc., but these film thicknesses are very thin. . For this reason, even if it is partially located under the mask 2, the adhesion between the mask 2 and the substrate 1 is not impaired.

[Step shown in FIG. 1B]
Subsequently, by performing SAM treatment, the protective film 4 is chemically adsorbed on the surface of the portion of the substrate 1 exposed from the mask 2, that is, the desired position where the protective film 4 is to be formed and the surface of the mask 2. SAM3 that encourages the user to be executed is formed. For example, the base material 1 on which the mask 2 is disposed is put into a film forming chamber, and SAM processing is performed in a vacuum (depressurized atmosphere) at a temperature at which the mask 2 is not deformed (for example, 50 ° C. or less). Although the degree of vacuum at the time of SAM treatment is arbitrary, a lower vacuum is preferable because a mean free process is shorter than that at the time of forming a protective film 4 described later.

  Specifically, surface treatment using a coupling agent having a reactive group (bonding hand) that reacts with a hydroxyl group (OH group) and a reactive group (bonding hand) that reacts with the material of the protective film 4 described later, for example, a cup The SAM treatment is performed by spraying a gas containing a ring agent onto the position where the SAM 3 is to be formed. This reacts with the hydroxyl groups on the surface of the substrate 1 and the surface of the mask 2 formed by moisture in the atmosphere and is chemisorbed accurately on these surfaces, while the desired position on the surface of the substrate 1 and the mask 2 A SAM 3 having a reactive group that reacts with the material of the protective film 4 is formed on the surface.

Examples of such a coupling agent include oxygen as a reactive group (bond) that reacts with a hydroxyl group and an amino group (NH ₂ ) as a reactive group (joint) that reacts with the material of the protective film 4. The silane coupling agent which has can be used. By performing surface treatment using such a silane coupling agent, for example, as shown in FIG. 3, a bond in which oxygen is arranged reacts with a hydroxyl group to cause chemical reaction on the surface of the substrate 1 or the surface of the mask 2. While adsorbed, SAM3 in which the desired position on the surface of the substrate 1 and the surface of the mask 2 are terminated with an amino group can be formed.

  Note that the process for forming the SAM 3 is basically a temperature lower than the temperature in the process of forming the protective film 4 to be described later, preferably a temperature that does not change with respect to the process of FIG. It can be performed at room temperature. In this case, since no gap is generated between the surface of the substrate 1 and the mask 2 until this step, the SAM 3 does not wrap around between the substrate 1 and the mask 2.

[Step shown in FIG. 1 (c)]
Thereafter, the protective film 4 is formed on the surface of the SAM 3 by, for example, the ALD method using a gas containing the material of the protective film 4. Specifically, when a silane coupling agent having an amino group is used as a termination structure on the surface of SAM3, for example, a coupling agent when forming SAM3, in addition to terephthalic acid dichloride that reacts with the amino group, ethylene Glycol and ethylenediamine are used. Then, by alternately spraying these, the terephthalic acid dichloride reacts with the amino group on the surface of SAM3 and is chemically adsorbed on the surface of SAM3, and the protective film 4 can be formed on the surface of SAM3.

  At this time, since the surface of the SAM 3 formed on the surface of the substrate 1 or the surface of the mask 2 is terminated by a reactive group that reacts with the material of the protective film 4, the surface of the SAM 3 is protected. The protective film 4 is formed by chemical adsorption of the material of the film 4.

  At this time, when the gas containing the material of the protective film 4 is blown, there is a case where the temperature of the base material 1 is increased to, for example, about 100 ° C. by heating, and there is a gap between the base material 1 and the mask 2. May occur. However, since the material of the protective film 4 is not chemically adsorbed as the material of the base material 1, even if the gas containing the material of the protective film 4 wraps around the gap between the base material 1 and the mask 2. The protective film 4 is not formed on the surface of the substrate 1 in the portion where the SAM 3 is not formed.

  Therefore, the protective film 4 is formed only on the desired position where the protective film 4 is to be formed on the surface of the substrate 1 and the SAM 3 formed on the surface of the mask 2, and the substrate is not formed on the portion where the SAM 3 is not formed. The protective film 4 can be prevented from being formed on the surface of 1. Thereafter, the mask 2 is removed from the base material 1 to complete an organic EL device having an organic EL element in which a desired position on the surface of the base material 1 is covered with a protective film 4.

  As described above, in the present embodiment, the mask 2 in which the region where the protective film 4 is to be formed is opened on the base material 1 provided with the organic EL element, and then the mask 2 on the surface of the base material 1. SAM3 is formed on the exposed part of the mask and the surface of the mask 2. Thereafter, a protective film 4 is formed on the surface of the substrate 1 on which the SAM 3 is formed and the surface of the mask 2 using a gas.

  As the base material 1, a material to which the mask 2 is brought into close contact and the SAM 3 is chemically adsorbed and the material of the protective film 4 is not chemically adsorbed is used. Further, as the mask 2, a material that is chemically adsorbed by the SAM 3 while being in close contact with the base material 1 is used. Further, as the protective film 4, a material that is chemically adsorbed by the SAM 3 and is not chemically adsorbed by the base material 1 is used.

  For this reason, even when a gap is formed between the base material 1 and the mask 2 when the protective film 4 is formed and gas flows into the gap, the protective film 4 is not formed on the surface other than the surface of the SAM 3. Can be. Further, the protective film 4 is also formed on the mask 2, but the SAM 3 is formed on the surface of the mask 2, the SAM 3 is chemisorbed on the mask 2, and the protective film is applied to the SAM 3. Since 4 is in a chemically adsorbed state, the protective film 4 is difficult to peel off from the mask 2. Therefore, since the protective film 4 formed on the mask 2 is peeled off and becomes a foreign substance, it does not cause deterioration of the characteristics of the organic EL device, so that the mask 2 can be repeatedly used.

  Therefore, the protective film 4 can be accurately formed at a desired position by the manufacturing method of the present embodiment. It is also possible to prevent the protective film 4 formed on the mask 2 from peeling off from the mask 2 and becoming a foreign substance.

(Other embodiments)
The present invention is not limited to the embodiment described above, and can be appropriately changed within the scope described in the claims.

  For example, in the above embodiment, a glass substrate, a silicon substrate, or a polyimide substrate is used as the base material 1, and glass, SUS, or a resin is used as an example of the material of the mask 2. Further, SAM3 is exemplified by a silane coupling agent having oxygen or an amino group as a reactive group (bonding hand), and terephthalic acid dichloride as a material of the protective film 4.

  However, (1) the material of the substrate 1 is a material to which the mask 2 is brought into close contact and the SAM 3 is chemically adsorbed and the material of the protective film 3 is not chemically adsorbed. (2) The material of the mask 2 is SAM3 is a material that is chemically adsorbed while being in close contact with the substrate 1, and (3) the material of the protective film 4 is a material that is chemically adsorbed to the SAM3 and not chemically adsorbed to the substrate 1. Any combination is possible.

Further, the protective film 4 may not be a single layer film, but may have a stacked structure as a role of a film stress relaxation film formed by stacking with, for example, Al ₂ O ₃ .

  In addition to protecting the surface of the organic EL element, the protective film 4 may be used for other purposes, for example, when covering an arbitrary place of the base material 1 as a gas barrier layer when an inexpensive resin substrate is used as the base material 1. Applicable ones are listed.

  In the present specification, the terms “material that is chemically adsorbed” or “material that is not chemically adsorbed” are used to describe the materials of the substrate 1, the mask 2, the SAM 3, and the protective film 4. In other words, the “material that is chemisorbed” can be said to be a material that is easily chemisorbed. In other words, the “material that does not chemisorb” can be said to be a material that is difficult to chemisorb. Materials that are difficult to chemisorb do not exclude the case where they are not completely chemisorbed. Materials that have a low probability of chemisorption or require a long time for chemisorption or chemisorption compared to materials that are easily chemisorbed. Even if it does, it means that it is a material which peels easily. Even if it is a material that is chemically adsorbed, if the gas concentration at the time of use is set to 1/10 of the usual, if the probability of chemical adsorption becomes small or it takes a long time for chemical adsorption, use it at that gas concentration. In some cases, it will be included in materials that are difficult to chemisorb.

1 base material 2 mask 3 SAM
4 Protective film

Claims (5)

After the formation process of the self-assembled monolayer (3) is performed on the base material (1) provided with the organic EL element, the protective film (4) is formed at a desired position on the surface of the base material using a gas. An organic EL device manufacturing method for forming
A step of preparing the base material made of a material in which the material of the protective film is not chemisorbed, the material of the self-assembled monolayer is chemisorbed, and the mask adheres;
Placing the mask made of a material on the surface of the substrate where the desired position on the surface of the substrate is opened and the material of the self-assembled monolayer is chemisorbed;
Forming the self-assembled monolayer that promotes chemical adsorption of the material for forming the protective film on the surface at a desired position on the surface of the substrate and the surface of the mask;
Using a gas containing a material of the protective film made of a material that does not chemisorb to the substrate and chemisorbs to the self-assembled monolayer, a desired position on the surface of the substrate and And a step of forming the protective film on the surface of the self-assembled monolayer formed on the surface of the mask.   2. The method of manufacturing an organic EL device according to claim 1, wherein in the step of forming the protective film, a material that is not chemically adsorbed by a hydroxyl group is used as the material of the protective film.   3. The method of manufacturing an organic EL device according to claim 1, wherein the step of forming the self-assembled monolayer is performed at a lower temperature than the step of forming the protective film. In the step of preparing the base material, glass or polyimide is used as the base material,
In the step of setting the mask, a resin is used as the mask,
The step of forming the self-assembled monolayer uses a coupling agent having a hydroxyl group and a reactive group that reacts with the material of the protective film as the material of the self-assembled monolayer. The manufacturing method of the organic electroluminescent apparatus as described in any one of 1-3.   5. The method of manufacturing an organic EL device according to claim 1, wherein in the step of forming the protective film, an ALD method is used as a film forming method using the gas.

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