WO2006093193A1

WO2006093193A1 - Metal pattern, organic electronic device and process for producing the same

Info

Publication number: WO2006093193A1
Application number: PCT/JP2006/303887
Authority: WO
Inventors: Tsuyoshi Tsujioka; Shinichiro Nakamura
Original assignee: Mitsubishi Chemical Corporation
Priority date: 2005-03-02
Filing date: 2006-03-01
Publication date: 2006-09-08

Abstract

It is intended to form an electrode pattern of organic device with free morphology and with high precision without being placed under various restraints accompanying the steps of metal mask preparation, formation of overhanging line bulkhead, detachment with adhesive film, etc. There is provided a process for producing an organic electronic device wherein voltage is applied to a layer of organic electronic material to thereby cause the same to function, which process comprises forming a foundation layer containing an optionally substituted 1,2-diarylethene, realizing an isomerization reaction in given pattern of the 1,2-diarylethene of the foundation layer, and thereafter applying an electrode material on the foundation layer to thereby form an electrode pattern corresponding to the given pattern. The adherence of magnesium, etc. as the electrode material is changed by the isomerization reaction of the 1,2-diarylethene, and further by the induction of the isomerization reaction, a striking difference between magnesium adherence and nonadherence is brought about when the ratio between open-ring molecules and closed-ring molecules at relevant portion exceeds a certain value. Thus, patterning can be accomplished.

Description

Specification

Metal pattern, organic electronic device and manufacturing method thereof

Field of Invention

The present invention relates to a metal pattern manufacturing method, a metal pattern, and an electrode and an electric circuit using the metal pattern. The present invention also provides organic electoluminescence (hereinafter

The present invention relates to various organic electronic devices using organic materials, such as displays and thin film transistors (hereinafter referred to as `` organic TFTs ''), and methods for manufacturing such organic electronic devices. .

Background of the Invention

[0002] In recent years, organic electronic devices such as organic EL displays that sandwich organic thin films with electrodes and inject current by applying voltage between the electrodes to use light emission and other functions. Research and development is active.

[0003] Among these organic electronic devices, the organic EL display device includes a first electrode made of a transparent conductor such as ITO provided on a glass substrate, a hole transport layer provided on the first electrode, It consists of an organic layer with a powerful multilayer structure such as an electron transport layer and a light emitting layer, and a second electrode such as A1 and Mg provided on the organic layer. Generally, in a display device or the like, since it is necessary to control light emission (color and intensity) for each pixel, an electrode pattern corresponding to each pixel is formed. For example, an ITO anode (first electrode) patterned in advance on a glass substrate is used, and if necessary, each pixel is coated by vapor deposition using an organic material strength S metal mask. The second electrode can also be formed by other methods with a force that may be patterned by a metal mask.

[0004] For example, Patent Document 1 discloses a method for forming a cathode pattern of a nossive organic EL display. In the method disclosed in Patent Document 1, as described in FIG. 14 of Patent Document 1, an overhanging line partition wall is provided in advance on a substrate, and an organic layer and a cathode metal are deposited thereon. Due to the effect of barrier overhang, the cathode is separated by the barrier during deposition, and a line cathode is automatically formed. That's it. However, this method requires the provision of barrier ribs on the substrate in advance, which complicates the manufacturing process and has a problem that the degree of freedom in patterning of the cathode is small.

[0005] Further, Patent Document 2 discloses a method in which a cathode is deposited on the entire surface of an organic layer, and then a film coated with an adhesive material corresponding to a desired pattern is applied and peeled off. However, in this method, only the electrodes are not always peeled into a desired pattern, and depending on the adhesive, the organic layer may be damaged.

Patent Document 1: JP-A-8-315981

Patent Document 2: JP 2004-79373 A

Summary of the Invention

[0006] The present invention has been made in view of the above-described conventional circumstances, and the object thereof is to create various metal masks, formation of overhanging line partition walls, peeling with an adhesive film, and the like. The purpose is to provide a technology for forming metal patterns such as electrode patterns of various organic electronic devices including the above-mentioned organic EL display devices in a free shape without being caught by constraints.

[0007] The method for producing a metal pattern of the first aspect is a method of producing a metal pattern on a substrate. A material whose physical properties are changed by light on the substrate (hereinafter referred to as "photosensitive material"). Forming a layer including a layer, forming a pattern of physical property change of the photosensitive material by irradiating the layer including the photosensitive material with light, and stacking a metal on the pattern to form a metal pattern Forming the step.

[0008] A method for producing a metal pattern of a second aspect is a metal pattern formed on a substrate, wherein a layer containing a photosensitive material is provided between the metal layer forming the metal pattern and the substrate. It is characterized by having.

[0009] The organic electronic device of the third aspect is an organic electronic device having a first electrode and a second electrode, and an organic layer provided between these electrodes, and is between the first electrode and the organic layer. In addition, at least one portion between the second electrode and the organic layer has a layer containing 1,2-diarylethenes which may have a substituent in which a non-turn having a different isomerization state is formed. It is characterized by doing. [0010] An organic electronic device of a fourth aspect is an organic electronic device having a substrate, a first electrode, an organic layer, and a second electrode, wherein the first electrode and the organic layer are interposed between the substrate and the first electrode. And a layer containing 1,2-diarylethene which may have a substituent, in which at least one portion between the second electrode and the organic layer is formed with a pattern having a different isomerization state. It is characterized by having.

[0011] The organic electronic device manufacturing method of the fifth aspect may have a substituent compared to the method of manufacturing an organic electronic device that functions by applying a voltage to a layer made of an organic electronic material. An electrode material is applied on the underlayer by a step of forming an underlayer containing 1,2-diarylethene, a step of subjecting the 1,2-diarylethene of the underlayer to an isomeric reaction in a predetermined pattern, and the following. And forming an electrode pattern corresponding to the predetermined pattern.

Brief Description of Drawings

[0012] FIG. 1 is a photograph showing the isomeric state of DAE and the adhesion state of magnesium in Experimental Example 1, and FIG. 1 lb is an absorption spectrum showing the ratio of ring-closed molecules of DEA.

[FIG. 2] FIGS. 2a, 2b, 2c, and 2d are explanatory diagrams showing experimental methods in Experimental Example 3, respectively.

FIG. 3 is a micrograph showing an undeposited line of magnesium in Experimental Example 3.

FIG. 4 is a graph showing voltage-current characteristics of Samples 1 and 2 in Experimental Example 4.

FIG. 5 is a graph showing the voltage-current characteristics of Samples 3 and 4 in Experimental Example 4 and Sample 10 in Experimental Example 6.

[0013] The inventors of the present invention are 1,2-diarylethenes (hereinafter abbreviated as “DAE”), which is a kind of photochromic molecular material. In the present invention, DAE may have a substituent. In addition, materials that have substituents are also called “DAE”)), and other materials that change their physical properties by light, that is, light-sensitive materials are prominent depending on the state of physical property change such as their isomericity. It has been found that it has an affinity for metals such as magnesium. The inventor therefore pre-

By forming an underlayer of a photosensitive material such as AE, and changing the physical properties of the photosensitive layer such as DAE into a predetermined pattern such as isomorphism, it is very easy to It has been found that a metal pattern can be formed. The inventor further provides the DAE It has been found that by mixing a carrier transporting material in the underlayer of the photosensitive material such as DAE, it can be used as an underlayer of the photosensitive material such as DAE that also has excellent carrier transportability.

[0014] According to the present invention, an organic device can be formed in a free shape and with high accuracy without being caught by various constraints associated with processes such as formation of a metal mask, formation of overhanging line partition walls, and peeling with an adhesive film. It is possible to form a metal pattern such as an electrode pattern.

[0015] The metal pattern formed by the present invention can be used for various electronic and electrical equipment electrodes and electrical circuits.

Alternatively, it can be used as an electrode or an electric circuit of an organic electronic device such as an organic EL element, an organic TFT element, an organic memory element, or a semiconductor element.

[0016] Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the description of the following embodiments, and various modifications may be made within the scope of the gist thereof. Can do.

[0017] [Principle of metal pattern formation]

In the method for producing a metal pattern of the present invention, a substrate having a layer containing a photosensitive material that changes its physical properties by light is irradiated with light in a predetermined pattern, and the substrate is subjected to the light irradiation pattern according to the light irradiation pattern. By changing the physical properties of the light-sensitive material, the change in the physical properties controls the metal adhesion or film-forming property, and the metal pattern is formed into a free shape.

[0018] The mechanism for controlling the adhesion or film-forming property of the metal by changing the physical properties of the light-sensitive material is the metal that has reached the substrate surface on which the metal is to be formed, as shown in the following experimental examples. It is based on the state of mutual molecular motion between atoms (mainly given by vapor deposition mainly in industry) and the substrate surface.

0 Adhesion and deposition of metal atoms on the surface of the substrate proceeds, resulting in film formation or

ii) Metal atoms can be dissipated without being deposited and deposited on the substrate surface, resulting in no film formation

Thereby, the metal film-forming property is controlled.

That is, if the surface of the substrate on which the metal is deposited is firm, It is thought that metal atoms that have lost a large amount of energy move around the surface of the substrate with surplus energy, and the frequency with which they contact the metal atoms that follow. The metal atoms then contact and bond with subsequent metal atoms on the substrate to form a mass, thereby losing little kinetic energy on the substrate and stabilizing, resulting in the metal on the substrate. The deposition and film formation progress.

[0020] On the other hand, if the substrate surface is extremely soft, metal atoms that have reached the substrate surface lose some energy due to collision with the substrate, but the loss energy is small and still has a high level of energy. Because of this, it moves actively. Since the subsequent metal atoms are similarly active, the possibility that a metal lump is formed by contact between metal atoms having high energy regardless of the frequency of collision between metal atoms is that the above-mentioned substrate surface is Expected to be less than the hard case. As a result, in such a case, metal film formation does not proceed.

Considering whether the substrate surface is soft! / Or firm! As the state of molecular motion in this way, it leads to whether the molecular motion on the substrate surface is active or not. In other words, it is the level of thermal motion on the substrate surface as seen from the metal atoms. When the substrate surface is soft, metal atoms actively move on the surface of the substrate, including the bulk state, and the metal atoms on the substrate surface rarely come into contact with each other due to their activity. . On the other hand, when the substrate surface is hard, the metal atoms are stably fixed on the substrate surface, and form clusters with neighboring metal atoms in the vicinity, further stabilizing.

[0022] As an element that determines the hardness and softness of the substrate surface (hereinafter, this physical property is referred to as "the dynamic structure of the substrate") that affects the ease of attachment and deposition of metal atoms. The glass transition temperature (Tg) of the substrate material, the morphology of the substrate surface, etc., but even with the same material, the dynamic structure changes by changing the temperature. In addition to the transition temperature and the surface shape of the substrate, it is considered that the metal adhesion and film formation can be controlled by controlling the dynamic structure of the substrate by the temperature of the substrate surface and the like.

[0023] In the present invention, metal adhesion or film formability is controlled by such a delicate balance between the dynamic structure of the substrate surface and the cluster formability of metal atoms to be deposited. There are parameters for controlling adhesion and film formation in the film formation operation and selection of materials. To do. By optimizing these parameters, according to the present invention, various metal patterns can be formed by controlling the adhesion or film forming properties of metals other than magnesium, such as aluminum and lithium, which will be described later.

[0024] One representative parameter is the material of the light-sensitive material-containing layer such as DAE, that is, the polymer medium that forms the light-sensitive material-containing layer, the substance impregnated therein, the metal species to be laminated, and Compatibility between them, temperature, etc.

[0025] By optimizing the parameters of the film formation conditions for the metal to be laminated, forming a light-sensitive material-containing layer on the surface of the substrate under the optimized conditions, and then laminating the metal after light irradiation. In addition, it becomes possible to form a metal pattern by controlling the adhesion or film-forming property of metal atoms.

[0026] In the following, the formation principle of the metal pattern in the present invention will be described by exemplifying a case where DAE that is isomerized by light irradiation is used as the photosensitive material. Photosensitive materials other than DAE are described below. Even in the case of using the patterning, it is possible to perform patterning by utilizing the fact that the adhesion property of the metal or the film forming property changes due to the change in physical properties of the photosensitive material due to light irradiation as described above.

[0027] DAE has two isomers: a closed ring state in which two aryl groups are bonded to form a ring containing a ethene double bond, and a ring-opened state in which these aryl groups are separated. Force Of these, magnesium does not adhere to the ring-open state, and magnesium adheres to the ring-closed state. In the present invention, by utilizing this property of DAE, for example, the electrode can be patterned as follows.

That is, a base layer containing DAE is formed on the organic layer of the substrate on which an organic layer for expressing the function of the device is formed in advance, and a pattern corresponding to a desired pattern is formed on the base layer. By irradiating light such as laser with a turn, an isomerized state portion of DAE is formed, and an electrode layer is formed thereon by evaporating, for example, magnesium. When the DAE in the formed underlayer is in a ring-opened state and becomes ring-closed due to isomerism, magnesium adheres to the isomerized state (ring-closed state) and the electrode pattern corresponding to the pattern Can be formed. In addition, when the DAE in the formed underlayer is in a closed ring state and becomes an open ring state by isomerization, the isomerized state (open ring state) portion is not included. Magnesium adheres to the outside, and an electrode corresponding to the negative pattern of the pattern can be formed. In this way, it is possible to easily form an electrode pattern with a pattern corresponding to the DAE isomorphism pattern.

[0029] The details of the mechanism by which electrode patterning can be performed by DAE isomerization in this way are not necessarily clear, but are estimated as follows. That is, due to some physical property change accompanying the isomerization reaction of DAE, the adhesiveness of magnesium changes, and the ratio between the ring-opened molecule and the ring-closed molecule of the part is caused by causing the isomeric reaction. When this value is exceeded, there is a significant difference between the adhesion and non-stickiness of magnesium, and patterning is considered possible. DAE can achieve this effect even with ultra-thin films such as lnm, which has a film thickness equivalent to about one molecule. In addition, DAE has a micron-order isomeric pattern formed by focusing the laser. In contrast, an electrode pattern corresponding to the electrode pattern can be formed. Therefore, according to the present invention, an electrode pattern having an arbitrary shape including a fine pattern corresponding to a focused spot of the laser beam can be formed. Can be formed with high accuracy at the same accuracy as the scanning accuracy of the laser beam. If the filter is devised, the light works effectively only in the part where the laser intensity is high, and it is possible to create a pattern less than the restriction by the wavelength.

[0030] It should be noted that DAE is normally colorless in the ring-opened state and colored in the ring-closed state. Therefore, according to the present invention, DAE is in a closed state, and there is an advantage that a portion having magnesium adhesion can be confirmed in a spectrum corresponding to color.

In addition, DAE does not affect the organic layers and electrodes of organic electronic devices. By forming a DAE-containing layer, the functions of organic electronic devices are not impaired.

[0031] [Photosensitive material whose physical properties are changed by light]

The photosensitive material that changes its physical properties by light used in the present invention is not limited to DAE unless the gist thereof is changed.

Examples of the change in physical properties of the light-sensitive material due to light include photoisomerization and optical phase change.

[0032] Materials that are isomerized by light are not particularly limited as long as they induce changes in physical properties as described above, for example, DAE, azobenzene, spiropyran, spirooxazine spironaphthoxa. Various photochromic materials such as gin and fulgide can be used.

[0033] The material that changes phase by light may be any inorganic material that can be used for phase-change optical memory materials and that can change the physical properties by light stimulation. For example, it is possible to use a thermocomic material that can impart the above-mentioned physical property change by heat generated by light irradiation.

[0034] These photosensitive materials can be formed on the substrate not only by a dry process such as an evaporation method but also by a wet process such as a cast method, a spin coat method, an ink jet method, and other printing methods.

[0035] The layer containing the photosensitive material on the substrate may contain only one type or two or more types of photosensitive material, and polystyrene, MEH- PPV if necessary. It may contain one kind or two or more kinds of polymer media such as (poly (2-methoxy-5- (2,1-ethynolehexyloxy) p-phenylene-lene)).

[0036] [Metallic pattern manufacturing method]

In the method for producing a metal pattern of the present invention, after a layer containing a photosensitive material is formed on a substrate, the photosensitive material-containing layer is irradiated with light in a predetermined pattern to thereby improve the physical properties of the photosensitive material. When the metal is deposited on the light-sensitive material-containing layer after the light irradiation by utilizing the difference in the adhesion property of the metal due to the change in physical properties and the difference in film formability, Form.

[0037] That is, in the case where the adhesion property of the metal is increased due to the change in physical properties of the photosensitive material due to light irradiation, and the film forming property is improved, the metal adheres according to the light irradiated pattern to form a metal pattern. On the other hand, if the metal adhesion or film-forming property becomes low due to changes in the physical properties of the light-sensitive material due to light irradiation, the metal will adhere to areas other than the light-irradiated pattern, and the light irradiation pattern will be reduced. A negative metal pattern is formed.

In the present invention, the substrate on which the light-sensitive material-containing layer is formed is not particularly limited, and glass, plastic, metal, ceramic, and any other material can be used.

[0039] In addition, the photosensitive material-containing layer may be formed after forming a base layer for improving adhesion of the photosensitive material-containing layer and other functions on such a substrate.

[0040] The photosensitive material-containing layer includes the type of photosensitive material used and the concentration of photosensitive material in the layer. Depending on the thickness, the film is formed to a thickness that allows patterning by light irradiation.

[0041] There are no particular restrictions on the light irradiation conditions for the light-sensitive material-containing layer. To the extent that the light-sensitive material in the light-sensitive material-containing layer causes a clear change in physical properties such that a metal pattern can be formed. I just need it.

[0042] Examples of the metal used for forming the metal pattern include, but are not limited to, magnesium, aluminum, strong lithium, lithium, or an alloy containing one or more of these. The metal pattern is formed by depositing metal to a predetermined thickness by vapor deposition or the like on the photosensitive material-containing layer whose physical properties have been changed by light irradiation according to its application.

[0043] The metal pattern formed as described above has a photosensitive material between the substrate and the substrate, and is useful as an electrode and an electric circuit, particularly as an electrode and an electric circuit of an organic electronic device.

However, the metal pattern manufactured by the method of the present invention and the electrode, electric circuit, and organic electronic device prepared using the metal pattern may have a layer containing a photosensitive material as described above. After manufacturing the metal pattern, the layer containing the photosensitive material can be appropriately removed by transfer, washing, etc. In this case, the layer containing the photosensitive material is not included. Become.

[0045] [Organic electronic devices]

Hereinafter, the present invention will be described in detail by exemplifying a case where the method for producing a metal pattern of the present invention is applied to the production of an organic electronic device. The metal pattern according to the present invention is not limited to any organic electronic device. It is not limited to what is used for.

[0046] The organic electronic device usually has a structure in which a first electrode, an organic layer, and a second electrode are laminated in this order, or further has a substrate on the first electrode side.

[0047] The organic electronic device of the present invention further includes

Between substrate and first electrode

Between the first electrode and the organic layer

Between the organic layer and the second electrode

Any one or more of them may have a substituent, such as 1, 2-diarylmethene It has a layer containing a responsive material.

That is, unlike the conventional organic electronic device, the organic electronic device of the present invention has a layer containing a light-sensitive material such as DAE between the electrode and the adjacent member. For the configuration of each member other than the layer containing the sensitive material and the formation method thereof, the conventional configuration and formation method of the organic electronic device can be applied. For example, the configuration described in Japanese Patent Application Laid-Open No. 2004-362930, Japanese Patent Application Laid-Open No. 2004-359671, Japanese Patent Application Laid-Open No. 2004-431587, etc. is arbitrarily selected and adopted. be able to. In addition, a configuration described in an organic organic transistor, such as Japanese Unexamined Patent Publication No. 2003-309268 and # ^ 2004-103638, can be arbitrarily selected and employed. Of course, it goes without saying that the content is not limited to those described in these publications.

[0049] However, the formation method of the first electrode and the second electrode can be arbitrarily selected within the range of the dry process without damaging the organic layer, such as vacuum deposition or sputtering. For electrodes to which patterning is applied due to changes in the physical properties of photosensitive materials such as 匕ヽ, because of the low damage to photosensitive materials such as DAE when metal atoms become electrodes It is preferable to employ vacuum deposition.

[0050] It should be noted that the substrate is not necessarily required for the organic electronic device of the present invention. If the first electrode and the organic layer as described later have sufficient thickness and strength, there is no substrate. It's all about composition.

Hereinafter, the light-sensitive material-containing layer, which is a characteristic part of the organic electronic device of the present invention, will be described with reference to the DAE-containing layer. The light-sensitive material according to the present invention is not limited to DAE. It is not a thing.

[0052] DAE

As the DAE that forms the DAE-containing layer according to the present invention, the compounds described in Irie et al., “Chemistry of Organic Photochemical Misumi”, Academic Publishing Center, 1996, and Japanese Laid-Open Patent Publication No. 2005-082507 are used. Force that can be used The present invention is not limited to these as long as selective adhesion with the electrode material such as magnesium described above is confirmed. Examples of the compound having selective adhesion to such an electrode material and having excellent radiation sensitivity include compounds represented by the following general formula (I). In particular, in the following general formula (I), a compound in which R ¹ and R ² are alkoxy groups is preferable because it causes less fading due to ambient light.

[Chemical 1]

In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

R ³ and R ⁴ are each independently a naphthyl group which may have a substituent, a styryl group which may have a substituent, a phenolic group which may have a substituent, or The substituted phenyl group represented by the following general formula (A) is shown.

[Chemical 2]

In the formula (A), R ⁹ has an alkoxy group which may have a substituent, an aralkyloxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent. An alkyl group that may be substituted, a phenoxy group that may have a substituent, or a substituent A phenyl group, an alkylamino group which may have a substituent, or an arylamino group which may have a substituent.

R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or an arbitrary substituent. However, among the groups described below as R ⁷ to R ^U, bonded to adjacent groups to, it may also have a substituent, to form a ring, even if good.

R ⁵ and R ⁶ each independently represents a hydrogen atom or an arbitrary substituent.

[0054] Hereinafter, the compound represented by the general formula (I) will be described in detail.

In the general formula (I), R ¹ and R ² are each independently a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group. An alkyl group having 1 to 4 carbon atoms such as a cyclobutyl group, or a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a cyclopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, An alkoxy group having 1 to 4 carbon atoms such as a cyclobutoxy group. Among them, an alkoxy group is preferred, and a methoxy group is particularly preferred without causing a problem of fading due to ambient light.

[0055] R ³ and R ⁴ each independently have a substituent! / May be !, a naphthyl group, an optionally substituted styryl group, and a substituent. A good phenyl group, or a substituted phenyl group represented by the general formula (A), of which a naphthyl group which may have a substituent, a phenyl group which may have a substituent, A luthul group or a substituted phenol group represented by the general formula (A) is preferred.

When R ³ or R ⁴ is represented by the general formula (A), R ⁹ is, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, ter Alkoxy groups having 1 to 10 carbon atoms such as t-butoxy group; aralkyloxy groups having 1 to 7 carbon atoms such as benzyloxy group, a-phenoxy group and β-phenethyloxy group; methylthio group and ethylthio group Alkylthio group having 1 to 10 carbon atoms such as propylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group; methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group Alkyl group having 1 to 10 carbon atoms such as isopropyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, hexyl group, etc .; phenoxy group; phenyl ; Mechiruamino group, dimethicone Alkylamino groups having an alkyl chain part having 1 to 6 carbon atoms, such as a ruamino group, a jetylamino group, a methylethylamino group; an arylamino group such as a phenolamino group, a diphenylamino group; a methylphenolamino group, etc. An alkylarylamino group; and the like. Each of the above-described groups may have a substituent, and the substituent is not particularly limited as long as it does not impair the performance of the compound represented by the general formula (I). As an example of R9, the aforementioned groups and halogen nuclear power are selected.

[0057] alkoxy group as the R ⁹ is an electron-donating among the group described above, Ararukiruokishi group, an alkylthio group, an alkyl group, phenoxy group, an alkylamino group, preferably is Ariruamino group member both of which are optionally substituted Also good. R ⁹ is more preferably an alkoxy group, an alkyl group, an optionally substituted phenoxy group, a dialkylamino group or a diarylamino group, and particularly preferably an alkoxy group.

[0058] R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or an arbitrary substituent. The optional substituent is not particularly limited as long as it does not impair the performance of the compound represented by the general formula (I), and examples thereof include the groups described above as examples of R ⁹ .

Of the R ^{7 to} R ^U groups, adjacent groups, that is, R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ^1Q , R ¹⁰ and R ¹¹ are bonded to form a ring. The ring which may be formed may have a substituent. When such a ring is formed, examples of the substituted phenol group represented by the general formula (A) include the following.

[0059] [Chemical 3]

[0060] The ring formed by bonding of adjacent groups among the forces R ^{7 to} R ^U that are not described in the above examples is an arbitrary group as long as the characteristics of the compound represented by the general formula (I) are not impaired. Examples of the substituent which may have a substituent include the groups described above as R ^{7 to} R ^U (when no ring is formed).

R ^{7 to} R ^U are preferably relatively electron donating groups as well as R ⁹ which is the p-position substituent of the general formula (A). Therefore, R ^{7 to} R ^U Preferred examples of the optional substituents corresponding to include the same groups as the preferred groups for R ⁹ and the ring formed by combining these groups.

[0061] In particular, R ⁷ and R ¹¹ are preferably hydrogen atoms. R ⁸ and R ^1Q are preferably hydrogen atoms, alkoxy groups, or alkyl groups U.

[0062] R ³ and R ⁴ forces may each independently have a substituent, may have a naphthyl group, have a substituent, may have a styryl group, or have a substituent! / In the case of representing a phenolic group, the substituent may be any substituent as long as the properties of the compound represented by the general formula (I) are not impaired. For example, the same groups as those exemplified as R ⁹ can be mentioned. Among them, an electron donating group is preferable as in R ⁹ , but is particularly preferable. Or an alkoxy group, an alkyl group, or a dialkylamino group.

R ³ and R ⁴ force each independently has a naphthyl group optionally having a substituent, may have a substituent, may have a styryl group, or have a substituent! / When it represents a pheuture group, it is most preferred that they are unsubstituted.

[0063] When R ³ and Z or R ⁴ have a substituent, and represent a naphthyl group, a 2-naphthyl group is more preferable as the naphthyl group.

R ³ and R ⁴ may have a substituent from the viewpoint of thermal stability and repeated durability, and are preferably a naphthyl group or a substituted phenyl group represented by the general formula (A).

[0064] R ⁵ and R ⁶ are each independently a hydrogen atom or an arbitrary substituent as long as the performance of the compound represented by the general formula (I) is not impaired! , But not too bulky

V is preferred, so hydrogen atom or methyl group is particularly preferred.

[0065] R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be the same or different, but the same is preferable.

[0066] The compounds represented by the general formula (I) represented by the general formula (I) preferably include, but are not limited to, the following compounds.

[0067] [Chemical 4]

(Me: methyl group)

(Me: methyl group)

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[0071] [Chemical 8]

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[0073] [Chemical 10]

[0074] [Chemical 11]

[0075] [Chemical 12]

[0076] The DAE-containing layer according to the present invention may contain only one kind of such DAE. Two or more kinds of DAE may be contained in any combination and in any combination ratio! / ヽOK!

[0077] Carrier transportable material

The DAE-containing layer according to the present invention has vapor deposition selectivity of an electrode material such as magnesium (usually a metal material described later) due to the DAE isomerism, but the DAE itself exhibits excellent carrier transportability. Not exclusively. For this reason, by providing a DAE-containing layer, even if the electrode pattern can be easily formed, the electron injection and transport characteristics (carrier transportability) may be deteriorated. In this case, the characteristics as a device are deteriorated. .

Therefore, it is preferable to mix carrier transporting material molecules in the DAE-containing layer according to the present invention for the purpose of enhancing carrier transportability. Mix DAE and carrier transporting material molecules By being present, a layer having both the deposition selectivity of the electrode material and excellent carrier transportability can be obtained.

[0078] The carrier transporting material is not particularly limited as long as it does not inhibit the properties of DAE. For example, Alq3 (aluminate-tris-8-hydroxyquinolate) which is a quinolinol complex of aluminum, _a- NPB (N, N di (naphthalene 1-yl) N, N, 1 diphenyl benzidene), organic molecules such as triphenylamine, polybutylcarbazole, MEH—PPV (polyphenylene bilene) Including polymer carrier transport materials such as, known ones can be used alone or in admixture of two or more.

[0079] Other ingredients

In the DAE-containing layer according to the present invention, other organic molecular materials, polymers, etc. may be arbitrarily selected within a range without impairing the properties of DAE. For example, a binder for improving film properties may be blended. Examples of binders include the usual polymer materials such as polystyrene. The above-mentioned polymer-based carrier transport materials also function as binders. These other components may be used alone or in combination of two or more.

[0080] Ratio of DAE etc. in DAE containing layer

The DAE-containing layer may be composed of only DAE. The carrier-transporting material as described above and other components may be included.

When the DAE-containing layer contains components other than DAE, if the proportion of DAE in the DAE-containing layer is excessively small, the intended purpose of the present invention cannot be achieved. In order to maintain the ratio, the proportion of DAE in the DAE-containing layer is usually 5% by weight or more, preferably 20% by weight or more, more preferably 45% by weight or more, and particularly preferably 50% by weight or more. .

[0081] The ratio of DAE in the DAE-containing layer is not necessarily the same in any part of the DAE-containing layer. The concentration distribution is generated in the thickness direction depending on the method of forming the DAE-containing layer. There may be.

[0082] When the DAE-containing layer contains a carrier transportable material, the ratio of the carrier transportable material in the DAE-containing layer is sufficient for maintaining the vapor deposition selectivity of the electrode material. It is necessary to set the ratio to exhibit. The specific carrier transportable material ratio is determined as appropriate depending on the V, the carrier transportability of the carrier transportable material, the carrier transportability required for the DAE-containing layer, etc. In order to obtain a sufficient carrier transport property while preventing the deposition selectivity of the electrode material of the DAE-containing layer from being deteriorated, the ratio of the carrier transportable material in the DAE-containing layer is usually 20% by weight or more. It is preferably 50% by weight or more, usually 90% by weight or less, preferably 80% by weight or less.

When carrier transporting material molecules are mixed, increase the carrier transporting material molecule ratio to improve carrier transportability, and then apply annealing treatment described later to develop deposition selectivity by DAE. It is preferable to enhance sex.

[0083] Film formation method

As a method for forming the DAE-containing layer according to the present invention, a dry process such as a vacuum deposition method or a sputtering method can be employed without any particular limitation.

[0084] As a method for forming a mixed layer of DAE and a carrier transporting material as a DAE-containing layer, for example, a binary evaporation method in which a deposition source of DAE and a carrier transporting material is separately prepared and heated independently. However, it is possible to prepare a single mixed source with a predetermined concentration in advance and put it in an evaporation boat in an amount that gives a predetermined film thickness. Can also be used. However, when a single mixed source is used, the carrier transporting material usually has a lower vapor pressure than DA E, so the DAE is deposited first and then the carrier transporting material adheres. In this case, sufficient DAE deposition selectivity may not be obtained for the formed DAE-containing layer.

[0085] In such a case, after the DAE-containing layer is formed, before the deposition of the electrode material, in particular, after the DAE-containing layer is formed and before the isomerization pattern is formed, the device is placed in a temperature environment higher than room temperature, for example. It is preferable to anneal for several hours. By performing such annealing treatment, the DAE and carrier transporting material molecules in the DAE-containing layer are appropriately mixed by thermal diffusion, and a thin film in which these are uniformly mixed can be obtained.

[0086] The annealing temperature is usually 30 ° C or higher, preferably 45 ° C or higher, usually 120 ° C. The temperature is preferably 100 ° C or lower. If the annealing temperature is too low, the mixing effect due to thermal diffusion is not sufficient, and on the contrary, if the annealing temperature is too high, the organic layer may be damaged if it has an organic layer in the DAE-containing layer or its lower layer. This is not desirable. The annealing time is not generally determined by the temperature conditions, but is usually about 30 minutes to 30 hours. In general, when the temperature is lower, it is preferable to shorten the time when the temperature is longer and higher, and the product of the processing temperature (° C) and the processing time (hour) ^ ~ 5 ° C · hours It is preferable that

[0087] Specifically, the annealing process is performed by storing the sample after forming the organic layer in a constant temperature bath set at a predetermined temperature so that the sample is not exposed to light for a predetermined period of time. It is desirable to carry out in a dry nitrogen atmosphere.

[0088] Film thickness

The film thickness of the DAE-containing layer according to the present invention is not particularly limited. The force varies depending on whether or not the DAE-containing layer contains carrier transportable material molecules and other components. Only DAE as shown in the examples below. In the case of the DAE-containing layer formed in (1), the patterning according to the present invention is possible even with a thickness of about 1 nm corresponding to the monomolecular layer. However, if the film thickness is excessively thin, a layer covering the entire DAE molecule cannot be formed, and the electrode layer adheres to this portion by locally exposing the underlying layer. Therefore, the lower limit of the film thickness is 1 nm or more, preferably 2 nm or more. With regard to the upper limit of the film thickness, if it is excessively thick, it may lead to undesired properties of DAE, for example, a material with low carrier transport capacity and low glass transition point, which may increase the operating voltage and deteriorate durability at high temperatures. Therefore, it is usually lOOnm or less, preferably 50 nm or less, more preferably 20 nm or less, and particularly preferably lOnm or less. However, when DAE itself has excellent carrier transportability and high glass transition point, there is no such upper limit of film thickness.

[0089] The film thickness when the DAE-containing layer contains carrier transporting material molecules and other components varies depending on the content of these mixed components. For the same reason as above, it is usually 1 nm or more, particularly 2 nm or more. In general, it is 200 nm or less, preferably lOOnm or less, more preferably 50 ηm or less, particularly preferably 20 nm or less, and particularly preferably lOnm or less.

[0090] In the organic electronic device of the present invention, DAE is a ring-opened state and a ring-closed state by isomerization. It is formed to perform electrode patterning by utilizing the difference in adhesion of the electrode material due to the difference in state. Accordingly, the DAE is formed between the electrode and another member. In addition, there is a closed DAE in the part corresponding to the patterned electrode pattern.

[0091] [Method for manufacturing organic electronic device]

The method for producing the organic electronic device of the present invention will be described in accordance with the operation procedure.

[0092] In the following, after the first electrode is formed on the substrate according to a conventional method, an organic layer is formed thereon, and DAE is contained for patterning the second electrode formed on the organic layer. The method of the present invention will be described by exemplifying the case where the second electrode is formed in a predetermined pattern shape by forming a layer, but the present invention is not limited to this method.

0 A method of forming a DAE-containing layer on a substrate, forming an isomerization pattern for the DAE-containing layer, forming a first electrode following the pattern, and further forming an organic layer and a second electrode

ii) In the above method 0, the second electrode is also patterned by forming an isomerization pattern of the DAE-containing layer on the organic layer as described later.

iii) A DAE-containing layer is formed on one or both sides of an organic layer having sufficient thickness and strength, and the first electrode and / or the second electrode is turned by forming an isomerization pattern of the DAE-containing layer. Method

The electrode patterning can be performed in various ways.

The patterning of the second electrode can be performed according to the following steps [1] to [5].

[1] A step of forming a first electrode on a substrate according to a conventional method.

[0094] A step of forming a predetermined organic layer on the first electrode according to a conventional method.

[0095] [3] A step of forming an underlayer containing the aforementioned DAE.

Here, the underlayer is preferably formed by a vacuum deposition method, a sputtering method, or the like, but when forming by a wet method such as a doctor blade method, a cast method, a spin coating method, or a dipping method, DAE is diluted with a solvent. It is desirable to prepare a coating solution and use this coating solution . In this case, the type of solvent is not particularly limited as long as it does not attack the organic layer.

Here, when the carrier transporting material molecules are further mixed in the DAE-containing layer, as described above, the carrier transporting material is formed together with the DAE by the binary evaporation method or the like. In the case of a wet method, a coating solution may be prepared by dissolving a carrier transporting material together with DAE in a solvent.

[0096] In the case where the underlayer containing this DAE is a layer consisting only of DAE, as described above, it is usually at least 1 nm, preferably at least 2 nm, usually at most lOOnm, preferably at most 50 nm, particularly at most lOnm. It is formed. In the case of an underlayer in which DAE, a carrier transporting material molecule and other components are mixed, as described above, usually 1 nm or more, particularly 2 nm or more, usually 200 nm or less, preferably lOOnm or less, more preferably It is formed to a thickness of 50 nm or less, particularly preferably 20 nm or less, particularly preferably lOnm or less.

[0097] After the formation of the DAE-containing layer, the annealing treatment described above is performed as necessary.

[0098] [4] A step of causing an isomeric reaction of DAE in the underlayer in a predetermined pattern.

As a method for causing this isomeric reaction, a method by irradiation with light is simple and preferable because of high patterning accuracy. That is, DAE used in the present invention is generally isomerized from a ring-opened state to a ring-closed state by irradiation with ultraviolet light in a wavelength region of 300 to 430 nm, particularly 300 to 400 nm, and 450 to 600 nm, especially 500 Irradiation with light of ˜600 nm causes isomerization from the closed ring state to the open ring state.

Therefore, using this property, it is preferable to cause DAE isomerism in a predetermined pattern in the underlayer according to the following method <A> or <B>, for example.

[0099] <A> The ultraviolet ray in the wavelength region of 300 to 430 nm, particularly 300 to 400 nm, is entirely irradiated to the underlayer containing DAE so that the DAE of the underlayer is entirely closed. Thereafter, light of 450 to 600 nm, particularly 500 to 600 nm, is irradiated to a predetermined pattern by laser spot scanning, and the DAE in the irradiated portion is isomerized to the ring-closing state force and the ring-opening state. This forms an underlayer in which the DAE ring-opened molecules exist in a predetermined pattern shape in the DAE ring-closed molecule matrix. Note that when the entire underlayer is in a closed state, the first entire surface irradiation step can be omitted. [0100] <B> The DAE containing the DAE is irradiated with light in the wavelength region of 450 to 600 nm, particularly 500 to 600 nm, so that the DAE of the underlayer is fully opened. Thereafter, ultraviolet light of 300 to 430 nm, especially 300 to 400 nm, is irradiated to a predetermined pattern by laser spot scanning, and the DAE of the irradiated portion is isomerized to a ring-opening state force or a ring-closing state. This forms an underlayer in which the DAE ring-closing molecules exist in a predetermined pattern shape in the matrix of the DAE ring-opening molecules. If all the underlayers are in the ring-opened state, the first entire surface irradiation step can be omitted.

[0101] [5] A step of forming the second electrode on the underlayer subjected to the DAE isomerism reaction according to the predetermined pattern as described above.

This second electrode is preferably formed by a vacuum deposition method.

There are no particular restrictions on the constituent material of the second electrode, but materials that differ in adhesion due to the DAE isomerism are preferably used. For example, one or two metals such as magnesium, aluminum, calcium, and lithium are used. More than species.

[0102] The film thickness of the second electrode is not particularly limited as long as the electrode performance required in the application of the organic electronic device can be sufficiently exhibited, but is usually 50 nm or more, usually lOOnm or less. is there.

[0103] By depositing the electrode material on the underlayer on which the isomerization pattern is formed in this way, the electrode material selectively adheres to the portion of the underlayer where the DAE is in a closed state, and the DAE is opened. Since the electrode material does not adhere to the state portion, the second electrode can be formed in a predetermined pattern.

That is, in the case where the DAE ring-opening molecules are formed in a predetermined pattern by laser spot scanning by the method <A> described above, the predetermined pattern portion is an undeposited portion of the electrode material, A second electrode is formed on the other matrix portion. Further, in the case where the DAE ring-closed molecules are formed in a predetermined pattern by laser spot scanning by the method <B> described above, the predetermined pattern portion becomes a vapor deposition portion of the electrode material, and the second portion is formed in this portion. An electrode is formed.

[0105] According to such a method of the present invention, it is possible to perform patterning of ultrafine electrodes having a width of 450 nm or less, for example, 260 to 450 nm, with high accuracy. In general, laser The light spot can be narrowed to a very small spot having a diameter of 600 nm or less, for example, 260 to 450 nm. Therefore, by scanning such a small laser spot, the laser beam can be irradiated with a width corresponding to the spot diameter.

[0106] On the other hand, DAE is a force that electrode material does not adhere in the ring-open state and electrode material adheres in the ring-closed state. As shown in Experimental Examples 1 and 2 below, Even if it is not 100% ring-closed, depending on the type of DAE, for example, even if 50% or more is ring-closed, the electrode material will adhere. Therefore, for example, a laser beam including a part that has been closed by direct irradiation with laser light and a part that has been partially closed by the influence of laser light in the vicinity thereof. The spot diameter can be adjusted if the filter is further devised. For example, it is possible to spot only where the laser intensity is strong, and the closed molecular part of the DAE can be formed with a width less than the spot of the laser beam. For this reason, it is possible to form an ultrafine pattern having a width of 400 nm or less by attaching an electrode material to this portion.

[0107] Note that the above-described light irradiation is not limited to scanning by a laser spot, and it is also possible to use a light blocking mask and a mask together with spot scanning.

Further, in the present invention, the electrode patterning is not limited to the method using only the DAE isomorphism as described above, but by using another patterning means such as a separate metal mask in combination with higher accuracy and efficiency. Patterning can also be performed.

As described above, the first electrode, the organic layer, and the second electrode can be formed on the substrate to produce the organic electronic device of the present invention.

Example

[0109] Hereinafter, the present invention will be described more specifically with reference to experimental examples and examples. However, the present invention is not limited to the following examples, and various modifications may be made within the scope of the gist thereof. Can be implemented.

[0110] [Experimental examples and examples showing DAE electrode patterning function]

Experimental example 1

A DAE thin film with a film thickness of lOOnm was formed on a slide glass substrate by vacuum evaporation using DAE represented by the following structural formula. [0111] [Chemical 13]

(M e: methyl group)

[0112] Next, ultraviolet light with a wavelength of 365 nm was irradiated to the DAE thin film while changing the irradiation amount partially, and five stages of isomeric states were formed on the same DAE thin film. That is,

State 0 = all DAE molecules open

State 1 = about 20% of all DAE molecules are closed (about 80% open)

State 2 = about 50% of all DAE molecules are closed

State 3 = about 80% of all DAE molecules are closed

State 4 = Almost 100% of all DAE molecules are closed

It was. At this time, since DAE is colored by being in a closed state, the DAE thin film is colored partially different depending on the degree of isomerization.

[0113] Next, magnesium was vacuum-deposited on this DAE thin film to a thickness of lOOnm, and the adhesion state of magnesium was examined.

As a result, as shown in Fig. 1, it was found that when the ring-closing molecule was 50% or less (states 1 and 2), magnesium was not attached, and when the force was 80% or more (states 3 and 4), magnesium was attached. It was.

Fig. 1 also shows the absorption spectrum in each state for investigating the ring-closing molecular ratio.

[0114] Experimental Example 2

In Experimental Example 1, an experiment was conducted in the same manner except that the DAE represented by the following structural formula was used as the DAE.

[0115] [Chemical 14]

(Me: Mechi're group)

[0116] As a result, this DAE also shows magnesium adhesion in the ring-closed state and non-adhesiveness of magnesium in the ring-opened state, but the degree is different from the DAE used in Experimental Example 1, and all the ring-closed molecules are Magnesium was attached even at 50% of the molecules.

[0117] From these results, DAE shows selective adhesion of magnesium due to its isomeric state, but the ratio of ring-closed bodies showing magnesium adhesion is not absolute.

It can be seen that it differs depending on the AE.

[0118] Experimental Example 3

The adhesion experiment of magnesium to the DAE thin film was conducted according to the procedure shown in Fig. 2a to 2d. First, a 50 nm-thick DAE thin film 2 was formed on a glass substrate 1 in the same manner as in Experimental Example 1 (FIG. 2a).

[0119] The DAE thin film 2 was irradiated with ultraviolet light 3 with a wavelength of 365 nm over the entire surface to form a colored state (ring-closed state) (Fig. 2b), and then a red laser with a wavelength of 650 nm (power lmW) 4 with a diameter of 10 The surface of the DAE thin film was scanned in a line shape with a spot of about μm and erased to form an isomerization pattern 5 (Fig. 2c). That is, a ring-opening molecule line was formed in the ring-closing molecule. After that, magnesium was vacuum-deposited on this DAE thin film 2 to a thickness of lOOnm (Fig. 2d) and observed with a microscope. As a result, the isomerization pattern (line of ring-opened molecules) shown in Fig. 3 was obtained. A corresponding magnesium undeposited line (about 15 m wide) was formed!

[0120] When the above magnesium adhesion experiment was performed on a DAE thin film with a thickness of 1 nm, which is the level of a single molecular layer of DAE, the DAE thin film with a thickness of a single molecular layer was used. However, it was confirmed that there was selectivity for magnesium adhesion. [0121] Example 1

The present invention was applied to an organic EL element, which is a typical organic electronic device, to form a magnesium cathode.

[0122] A copper phthalocyanine layer was formed as a hole injection layer on an ITO (Indium Tin Oxide) substrate to a thickness of 2 nm, and an α-NPB layer was formed as a hole transport layer thereon to a thickness of 30 nm. On top of this, an aluminum quinolinol complex Alq3 layer with a film thickness of 30 nm was formed as a light-emitting and electron transport layer. The DAE thin film used in Experimental Example 1 was deposited on this Alq3 layer to a thickness of 1 nm to form a DAE thin film. Then, in the same manner as in Experimental Example 3, the DAE thin film was irradiated with ultraviolet rays for 10 minutes to bring the DAE-containing layer into a closed state, and then the ring-opened state with a width of 15 m was detected by spot scanning with a red laser having a wavelength of 650 nm. The pattern was formed in a linear shape and a zigzag shape. After that, magnesium was vacuum-deposited on the DAE thin film to a thickness of lOOnm and observed under a microscope. A magnesium undeposited pattern corresponding to the pattern that was scanned by a laser and subjected to an isomeric reaction was formed. It was confirmed that magnesium was deposited.

[0123] Next, using the ITO of the substrate as the anode and the formed magnesium deposited film as the cathode, voltage was applied between the two electrodes, current injection was performed, and the state of light emission was observed from the ITO side, scanning with a red laser. It was confirmed that a non-light emitting pattern was formed corresponding to the pattern.

[0124] In this example, the magnesium non-adhering pattern was formed by red laser scanning. However, a colored line (ring opening body force is also isomerized to ring closure) was formed by scanning with an ultraviolet laser, and this scanning was performed. In the same way, it was possible to pattern the electrodes of organic EL elements by using a magnesium adhesion pattern shaped like the pattern.

[0125] [Experimental example showing improvement in carrier transportability when DAE is used in combination with carrier transportable material]

Example 4

The following experiment was conducted to evaluate the carrier transportability of the DAE used in Experimental Example 1.

A-NPB, which is a hole transport material, and Alq3, which is a typical electron transport material, are deposited by vacuum evaporation on an ITO substrate that has been cleaned with acetone and UV ozone. A film was formed on OOnm. Next, a total of four samples were prepared on these samples that were not DAE vacuum-deposited to a thickness of lnm. That is, the following Sampnole 1-4. For Sampnole 1 and 3, after DAE was colored by ultraviolet irradiation, a magnesium electrode with a film thickness of 200 nm was deposited on all samples.

Sample 1: ITO substrate Z a NPB layer ZDAE-containing layer

Sample 2: ITO substrate Z a NPB layer

Sample 3: ITO substrate ZAlq3 layer ZDAE containing layer

Sample 4: ITO substrate ZAlq3 layer

First, voltage-current characteristics of α-NPB samples 1 and 2 were examined using the ITO side as an anode and the magnesium side as a cathode. a NPB is much more excellent in hole transport than electron transport, and the current that flows is considered to be mostly due to holes. As a result, as shown in Fig. 4, almost the same voltage-current characteristics were obtained regardless of the presence or absence of the DAE-containing layer. This indicates that the DAE-containing layer affects the hole conduction.

[0127] Next, the voltage-current characteristics of Alq3 samples 3 and 4 were examined in the same way. As shown in Fig. 5, sample 3 with the DAE-containing layer had a much larger current than sample 4 without. Declined. Since Alq3 is much better in electron transport than hole transport, it can be considered that the current that flows is mostly due to electrons. This indicates that the injecting and transporting characteristics have been greatly deteriorated.

[0128] Experimental Example 5

By providing a DAE-containing layer, even if the patterning of the cathode can be easily performed, there is a risk that the characteristics as a device will deteriorate if the electron injection and transport characteristics deteriorate. Therefore, we next investigated the deposition selectivity and electron injection and transport characteristics of the electrode metal when a mixed layer of DAE and carrier transport material was formed.

[0129] DAEZA lq3 mixed source deposition source with DAE concentration of 75%, 50%, 25%, 10%, 5% by weight was prepared, and a film was formed on the glass substrate (film thickness 3nm). Samples 5-9 below with different DAE concentrations were prepared.

Sample 5: DAE concentration 75% by weight Sample 6: DAE concentration 50% by weight

Sample 7: DAE concentration 25% by weight

Sample 8: DAE concentration 10% by weight

Sample 9: DAE concentration 5% by weight

[0130] Immediately thereafter (without annealing), magnesium was deposited on the DAE-containing layer of each sample. At this time, the DAE is in a decolored state, and if the deposition selection function of the DAE appears, the magnesium cannot adhere.

As a result, the DAE concentration is 50 wt. It was found that deposition selectivity appeared only in samples 5 and 6 above.

[0131] Next, each sample formed into a film under the same conditions as above was annealed in a thermostatic chamber in a light-shielded state at 50 ° C for 2 hours, and then magnesium was similarly deposited. It was confirmed that the deposition selectivity of samples 5 to 7 with a DAE concentration of 25% by weight or more was exhibited, and that the annealing process was not performed! /, Lower than the case 1, and that the deposition selectivity of magnesium appeared at the DAE concentration. It was.

[0132] The reason why such a result was obtained is that, as mentioned above, the presence of Alq3 reduces the deposition selectivity of DAE, but by annealing, Alq3 and DAE are mixed uniformly by thermal diffusion. As a result, even if the DAE concentration is low, the deposition selectivity by DAE can be expressed.

Considering the electron transport properties, it is considered that the deposition characteristics at the lowest possible DAE concentration will improve the characteristics of the device. Therefore, it is desirable to perform annealing treatment in this way.

[0133] The vapor deposition selectivity (yes) or not (no) according to this experimental example is summarized in Table 1 below.

[0134] [Table 1]

Sample 5 6 7 8 Θ

DAE ¾ degree (% by weight) 75 50 25 10 5

No annealing process yes yes no no no

With annealing treatment yes yes yes no no [0135] The annealing conditions in this experimental example are only examples. However, if the processing is performed at an excessively high temperature, the organic layer itself may be damaged as described above, which is not desirable. It was confirmed that annealing at 30 ° C, which is a slightly higher room temperature, can achieve the same effect as above in about 24 hours.

[0136] Experimental Example 6

Next, the electronic properties of the mixed layer of DAE and Alq3 were evaluated.

As in Example 4, Alq3 was formed on the ITO substrate with a film thickness of lOOnm, and a mixed layer with a DAE concentration of 25% by weight was formed on it using a single deposition source with a DAE concentration of 25% by weight. Formed with. Next, after annealing at 50 ° C. for 2 hours, DAE was colored by irradiation with ultraviolet rays, and then a magnesium electrode was deposited to prepare Sample 10.

[0137] The voltage and current characteristics of this sample 10 were examined using the ITO side as the anode and the magnesium side as the cathode. As shown in the plot of sample 10 in Fig. 5, sample 4 of experimental example 4 was obtained. It was confirmed that a current comparable to that of (Alq3 single layer only, no DAE-containing layer) flows. This result shows that this configuration 'manufacturing process can realize an organic electronic device having a fine electrode pattern by vapor deposition selectivity and excellent electron injection and transport characteristics.

[0138] It should be noted that the present invention is not limited to organic EL devices, but can be applied to various organic electronic devices such as organic TFTs and organic memory devices. It is also clear that the DAE and carrier transporting material molecules used can be applied in the same manner as those other than the examples given here.

[0139] [Experimental example to examine the relationship between substrate surface temperature or glass transition temperature (Tg) and metal adhesion] Experimental example 7

MTDATA deposited by vacuum evaporation and represented by the following structural formula (starfastamine based on triphenylamine is starbust amine) (Tg = 76 ° C) and α—NPB (Tg = 95 ° C) With regard to the amorphous film, the surface temperature was changed as shown in Table 2, and magnesium was vacuum-deposited to determine whether magnesium was deposited. The results are shown in Table 2.

[0140] [Chemical 15]

[0141] [Table 2]

[0142] Experimental Example 8

Tg force of substrate material In order to investigate whether it has a significant effect on the adhesion of magnesium, magnesium was vacuum-deposited on the materials in Table 3 with different Tg, and the result of examining whether or not magnesium adhered Are shown in Table 3.

[0143] [Table 3]

From the above results, even if the surface of magnesium is the same material, the movement of metal atoms is inactive as the surface temperature is low. For materials with different Tg, it can be seen that the higher the Tg, the lower the Tg, and the lower the Tg!

[0145] Experimental Example 9

In order to investigate whether Tg of the substrate material has a significant effect on the adhesion of aluminum, which is another metal other than magnesium! / Aluminum was deposited on the materials in Table 4 by vacuum evaporation. Table 4 shows the results.

[0146] [Table 4]

From this result, it can be seen that aluminum has a sufficient force to adhere to a glass with a very high Tg, has a low Tg, is very soft at room temperature, and therefore has a high energy of metal atoms on the substrate surface and an active motion. It was clarified that although the surface of the surface was slightly larger than the adhesion of magnesium to silicon rubber, it hardly adhered (laminated).

[0148] From these results, it can be seen that if the suitability of the substrate is optimized for various metals, its adhesion or film-formability can be controlled.

[0149] Experimental Example 10

Polystyrene (styrene polymer), one of the representative polymers, or MEH—PPV (ADS100 RE, manufactured by American Dye Source, Inc), which is a typical high-molecular organic electronic material, displays the same DAE as used in Experimental Example 1. The samples were mixed at various concentrations shown in FIG. 5, dissolved in a cyclohexanone solvent, and prepared by forming a film with a thickness of 0.0 on a glass substrate by a casting method. Next, the sample was sufficiently irradiated with ultraviolet light (wavelength 365 nm) to form a colored state (ring-opened molecule), and then red laser light was collected and scanned to remove a 5 μm wide decoloring line ( Closed ring molecules). Magnesium was vacuum-deposited on this sample without using a mask, and it was examined whether or not a selective deposition phenomenon of magnesium would occur. The results are shown in Table 5.

[0150] In Table 5, selective indicates a selective deposition phenomenon, and a 5 μm wide magnetic field corresponding to the decoloring line. A non-adhesion line is formed, and not formed indicates that a selective vapor deposition phenomenon does not appear and magnesium is adhered to the entire surface.

From Table 5, DAE is 5% by weight for styrene polymer, and DAE is 10% for MEH-PPV.

It was found that the selective deposition phenomenon appears in%.

Examining various other polymers, it was found that such a phenomenon began to appear at concentrations of DAE of 1 to 30% by weight and higher.

[0151] Next, a colored line having a width of 5 µm was similarly formed with a violet laser having a wavelength of 405 nm, with the DAE remaining in a decolored state without coloring the sample prepared in the same manner as described above. Although this DAE has a very low absorption at a wavelength of 405 nm! /, It has a high coloring sensitivity (quantum yield of the coloring reaction), so it can cause an isomeric reaction by violet laser irradiation.

When magnesium was vacuum-deposited on this sample without using a mask, the corresponding width was 5% by weight or more for DAE with styrene polymer and 10% by weight or more for DAE for MEH PPV, as in the case of forming the decoloring line. It was confirmed that a magnesium line of μm was formed.

Therefore, it was confirmed that even with DAE in a polymer material, it is possible to form a corresponding magnesium pattern by either pattern formation by decoloring or pattern formation by coloring.

[0152] [Table 5]

DAE concentration (wt%) Polystyrene MEH-PPV

0 not rormed not formed

5 formed not formed

10 formed formed

15 formed formed

20 formed formed

30 formed formed [0153] As a result, polystyrene is not used as an organic electronic material and has no electrical conductivity. However, when it is used as an electrical insulator around an electronic device, for example, isomerization reaction by laser scanning and subsequent maskless deposition. It shows that any minute electrical wiring pattern can be easily formed. Furthermore, it was found that MEH-PPV does not change its electron transport property even when doped with about 10% by weight of force D AE, which is an electron transport material. This indicates that this method can also be used as a cathode for polymer-based organic electronic devices.

[0154] As described above, this selective vapor deposition method using the DAE isomorphism reaction is used to form electrode patterns and wiring patterns of various organic electronic devices such as organic EL, organic TFT, and organic memory. I can do it.

[0155] Although the invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.

This application is a Japanese patent application filed on March 2, 2005 (Japanese Patent Application 2005-05).

7709) and Japanese patent applications filed on December 15, 2005 (Japanese Patent Application 2005-36200)

Based on 2), which is incorporated by reference in its entirety.

Claims

The scope of the claims

[I] In a method for producing a metal pattern on a substrate, a step of forming a layer containing a material whose physical properties are changed by light (hereinafter referred to as “photosensitive material”) on the substrate; The method includes a step of forming a pattern of physical property change of the photosensitive material by irradiating the layer containing the material with light, and a step of forming a metal pattern by laminating metal on the pattern. A method for producing a metal pattern.

[2] Claim 1! The method for producing a metal pattern is characterized in that the change in physical properties of the photosensitive material due to light is one of isomerization and phase change.

[3] The method for producing a metal pattern according to claim 2, wherein the photosensitive material is 1,2-diarylethene which may have a substituent which is isomerized by light.

[4] The method for producing a metal pattern according to claim 1, wherein the metal is at least one metal selected from the group consisting of magnesium, aluminum, potassium, and lithium.

[5] A metal pattern formed on a substrate, comprising a layer containing a photosensitive material between the metal layer forming the metal pattern and the substrate.

[6] An electrode having the metal pattern according to claim 5.

[7] An electric circuit having the metal pattern according to [5].

[8] An organic electronic device having the electrode according to claim 1.

[9] An organic electronic device having the electric circuit according to claim 7.

[10] An organic electronic device having a first electrode and a second electrode, and an organic layer provided between these electrodes, between the first electrode and the organic layer, and between the second electrode and the organic layer Organic electronic device comprising a layer containing 1,2-diarylethene which may have a substituent, in which at least one of the layers has a pattern with different isomeric states formed .

[II] An organic electronic device having a substrate, a first electrode, an organic layer and a second electrode, between the substrate and the first electrode, between the first electrode and the organic layer, and between the second electrode and the organic At least one of the layers may have a substituent formed with a pattern of different isomeric states 1,

An organic electronic device having a layer containing 2-diarylmethene.

[12] In Claim 10, at least one of the first electrode and the second electrode is provided with the 1, 2-dia. An organic electronic device comprising a pattern corresponding to a pattern having a different isomeric state of a layer containing Lilleweten.

[13] The method according to claim 11, wherein at least one of the first electrode and the second electrode includes a pattern corresponding to a different pattern of the isomeric state of the layer including the 1,2-diarylethene. And organic electronic devices.

14. The layer according to claim 10, wherein the layer contains 1,2-diarylethene which may have the substituent.

1S An organic electronic device characterized by being a layer in which 1,2-diarylethene, which may have a substituent, and a carrier transporting material molecule are mixed.

15. The layer according to claim 11, wherein the layer contains 1,2-diarylethene which may have the substituent.

1S An organic electronic device characterized in that it is a layer in which 1,2-diarylethene, which may have a substituent, and carrier transporting material molecules are mixed.

[16] In a method of manufacturing an organic electronic device in which a voltage is applied to a layer made of an organic electronic material to make it function, an underlayer containing 1,2-diarylethene that may have a substituent is formed. Forming an electrode pattern corresponding to the predetermined pattern by applying an electrode material on the base layer, and then subjecting the 1,2-diarylethene of the base layer to an isomeric reaction in a predetermined pattern. A process for producing an organic electronic device.

[17] In Claim 16, the step of forming an underlayer containing 1,2-diarylethene which may have a substituent may have 1,2-diarylethene which may have a substituent and carrier transportability. A method of manufacturing an organic electronic device, characterized in that it is a step of forming an underlayer in which material molecules are mixed.

[18] The method according to claim 16, wherein the base layer containing the 1,2-diarylethenes optionally having the substituent is formed, and the 1,2-dierlethenes of the underlayers are different in a predetermined pattern. A method for producing an organic electronic device, comprising the step of annealing the device at a temperature of room temperature or higher between the step of reacting.