JP4572370B2 - Organic electronic device and manufacturing method thereof - Google Patents

Description

  The present invention relates to various organic electronic devices using organic materials such as organic electroluminescence (hereinafter referred to as “organic EL”) displays and thin film transistors (hereinafter referred to as “organic TFT”), and such organic electronic devices. It is related with the manufacturing method.

  In recent years, research and development of organic electronic devices that use light emission and other functions, such as organic EL displays, sandwich organic thin films with electrodes and inject current by applying voltage between the electrodes. Has been done.

  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 and an electron transport layer provided on the first electrode. And an organic layer having a multilayer structure including a light emitting layer and the like, and a second electrode made of Al, Mg, or the like 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 an organic material is applied to each pixel by vapor deposition using a metal mask as necessary. The second electrode may be patterned by a metal mask, but may be formed by other methods.

  For example, Patent Document 1 discloses a cathode pattern forming method for a passive organic EL display. In the method disclosed in Patent Document 1, as described with reference to FIG. 14 of Patent Document 1, an overhanging line partition is provided on a substrate in advance, and an organic layer and a cathode metal are deposited thereon. The cathode is separated by the partition during the deposition due to the effect of the overhang of the partition, and the line-shaped cathode is automatically formed. However, in this method, it is necessary to provide a partition wall on the substrate in advance, and there are problems that the manufacturing process becomes complicated and the degree of freedom in patterning the cathode is small.

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 attached and peeled off. However, in this method, only the electrodes are not always peeled into a desired pattern, and the organic layer may be damaged depending on the adhesive material.
JP-A-8-315981 JP 2004-79373 A

  The present invention has been made in view of the above-described conventional circumstances, and its purpose is captured by various constraints associated with processes such as the creation of a metal mask, the formation of an overhanging line partition wall, and the peeling with an adhesive film. Therefore, it is desirable to provide a technique for forming electrode patterns of various organic electronic devices including the organic EL display device in a free shape.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that 1,2-diarylethene (hereinafter abbreviated as “DAE”), which is a kind of photochromic molecular material. In the present invention, DAE has a substituent. In the following, it is referred to as “DAE” including those having a substituent.) Has a remarkable magnesium affinity according to its isomerization state, and therefore, a DAE underlayer is previously formed. The electrode pattern can be formed very easily by isomerizing the DAE underlayer into a predetermined pattern. In this case, the magnesium affinity of the DAE underlayer is such that the DAE underlayer and the electrode layer even when forming an intermediate layer between, the intermediate layer is, it found that it is an effective if it is within a certain thickness, thereby completing the present invention.

  That is, this invention makes the following a summary.

(1) In 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 / or the second electrode and the organic layer between, for patterning the electrode by utilizing the difference in adhesion of the electrode material, an organic electronic device having a layer containing also a good 1,2 diarylethene substituted, the In the layer containing 1,2-diarylethene which may have a substituent, patterns with different isomerization states of 1,2-diarylethene which may have a substituent corresponding to the electrode pattern are formed by light irradiation. A layer on which electrode patterning is performed due to a difference in adhesion to an electrode material due to a difference in isomerization, between a first electrode and a layer containing 1,2-diarylethene, and / or a second electrode 1,2-diary An organic electronic device comprising a carrier-transporting intermediate layer between a layer containing ruethene.

(2) In 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 layer. An organic electronic device having a layer containing 1,2-diarylethene, which may have a substituent , for patterning an electrode by utilizing a difference in adhesion of an electrode material The layer containing 1,2-diarylethene which may have a substituent is different in the isomerization state of 1,2-diarylethene which may have a substituent corresponding to the electrode pattern by light irradiation. A layer in which a pattern is formed and electrode patterning is performed due to different adhesion to the electrode material due to differences in isomerization, between the first electrode and the layer comprising 1,2-diarylethene and / or Second electrode and 1,2- An organic electronic device comprising an intermediate layer capable of transporting carriers between a layer containing diarylethene.

(3) In the organic electronic device of (1) or (2), the first electrode and / or the second electrode include patterns corresponding to patterns having different isomerization states of the layer containing 1,2-diarylethene. An organic electronic device characterized by that.

(4) In a method of manufacturing an organic electronic device that functions by applying a voltage to a layer made of an organic electronic material, the adhesion with the electrode material may be different due to a difference in isomerization . A step of forming an underlayer containing 2-diarylethene, a step of isomerizing the 1,2-diarylethene of the underlayer in a predetermined pattern, and a step of forming an intermediate layer having a carrier transport property on the underlayer, Then, an electrode material is provided on the intermediate layer, and an electrode pattern corresponding to the predetermined pattern is formed.

  DAE has two isomers, a ring-closed state in which two aryl groups are bonded to form a ring containing an ethene double bond, and a ring-opened state in which these aryl groups are separated. In the ring-open state, magnesium does not adhere, and in the ring-closed state, magnesium adheres. In the present invention, using 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 laser or the like is formed on the base layer in a pattern corresponding to a desired pattern. By irradiating with light, an isomerized state portion of DAE is formed, and an intermediate layer having a specific thickness, for example, an electron transport layer is formed thereon, and then an electrode material, for example, magnesium is evaporated to form an electrode. Form. Then, even though the DAE underlayer and the magnesium layer are not in direct contact with each other, when the DAE in the formed underlayer is in a ring-opened state and becomes a ring-closed state by isomerization, the isomerized state ( Magnesium adheres to the (ring-closed state) portion, and an electrode pattern corresponding to the pattern can be formed. In addition, when the DAE in the formed underlayer is in a ring-closed state and becomes a ring-opened state by isomerization, magnesium adheres in addition to the isomerized state (ring-opened state) portion, and the negative of the pattern An electrode corresponding to the pattern can be formed. In this way, it is possible to easily form an electrode pattern with a pattern corresponding to the DAE isomerization pattern. In addition, by forming the intermediate layer on the DAE underlayer, it is possible to protect the DAE underlayer, maintain the shape, and improve the light emission efficiency.
It is also possible to form an isomerized state portion in the DAE underlayer by irradiating light from above after forming an intermediate layer such as an electron transport layer.

The details of the mechanism by which electrode patterning can be performed by isomerization of DAE as described above are not necessarily clear, but are estimated as follows. That is, by some change in physical properties due to isomerization reaction of the DAE, changes in the adhesion between have intermediate layers magnesium occurs, also by causing the isomerization reaction, and ring opening molecule of the partial When the ratio to the ring-closed molecule exceeds a certain value, it is considered that there is a significant difference between the adhesion and non-adhesion of magnesium, and patterning becomes possible. DAE can achieve this effect even with an ultra-thin film with a thickness equivalent to about 1 molecule, such as 1 nm. Furthermore, DAE can be used for micron-order isomerization patterns formed by focusing the laser. Therefore, according to the present invention, an electrode pattern of any desired shape including a fine pattern corresponding to a focused spot of the laser beam can be formed by laser. It can be formed with high accuracy at the same accuracy as the light scanning accuracy. If the filter is devised, the light works effectively only in the portion where the laser intensity is large, and it is possible to create a pattern less than the restriction by the wavelength.

Note that DAE is normally colorless in a ring-opened state and colored in a 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 a color.
Further, DAE does not affect the organic layer or electrode of the organic electronic device, and the function of the organic electronic device is not impaired by forming the DAE layer.

  According to the present invention, the electrode of the organic device can be freely formed and highly accurately without being trapped by various constraints associated with the steps such as the creation of a metal mask, the formation of an overhanging line partition, and the peeling with an adhesive film. A pattern can be formed.

  Hereinafter, embodiments of the organic electronic device and the manufacturing method thereof of the present invention will be described in detail. However, the present invention is not limited to the description of the following embodiments, and variously within the scope of the gist of the present invention. It can be changed and implemented.

[Organic electronic devices]
The organic electronic device of the present invention 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,
Between the substrate and the first electrode Between the first electrode and the organic layer Any one or more between the organic layer and the second electrode, a layer containing 1,2-diarylethene which may have a substituent (Hereinafter also referred to as “DAE layer”) and having an intermediate layer between the first electrode and the DAE layer and / or between the second electrode and the DAE layer.

  That is, the organic electronic device of the present invention is different from conventional organic electronic devices in that it has a DAE layer between an electrode and an adjacent member via an electrode-side intermediate layer, except for the DAE layer and the intermediate layer. With respect to the configuration of each member and the formation method thereof, the conventional configuration and formation method of an organic electronic device can be applied. For example, for the organic EL element, the configurations described in JP-A-2004-362930, JP-A-2004-359671, JP-A-2004-331587 and the like can be arbitrarily selected and employed. As for the organic transistor, a configuration described in JP-A-2003-309268, JP-A-2004-103638, or the like can be arbitrarily selected and employed. Of course, it goes without saying that the content is not limited to those described in these publications.

  However, the formation method of the first electrode and the second electrode can be arbitrarily selected within the range of a dry process that does not damage the organic layer, such as a vacuum deposition method or a sputtering method, but patterning by DAE isomerization according to the present invention. For the electrode to which is applied, it is preferable to employ vacuum deposition for the reason of low damage to DAE at the time of adhesion of metal atoms to be an electrode.

  In the organic electronic device of the present invention, the substrate is not necessarily required. As will be described later, when the first electrode and the organic layer have a sufficient thickness and strength, the substrate may be configured without the substrate.

<DAE layer>
The DAE layer, which is a characteristic part of the organic electronic device of the present invention, will be described below.
In the organic electronic device of the present invention, the DAE is formed in order to perform electrode patterning by utilizing the difference in adhesion of the electrode material due to the difference between the ring-opened state and the ring-closed state due to the isomerization. Accordingly, the DAE is formed so as to be interposed between the electrode and another member. In addition, ring-closed DAE exists in a portion corresponding to the patterned electrode pattern.

(DAE)
As the DAE for forming the DAE layer according to the present invention, compounds described in Irie et al., “Chemistry of Organic Photochromism”, Academic Publishing Center, 1996 can be used. It is sufficient that the selective adhesion with the electrode material such as magnesium described above is confirmed, and the present invention is not limited thereto.

  In the DAE layer according to the present invention, only one type of such DAE may be included, or two or more types of DAE may be included in any combination and in any combination ratio.

(Other ingredients)
In the DAE layer according to the present invention, other organic molecular materials or polymers may be optionally added within a range that does not impair the properties of DAE. For example, a binder for improving film properties may be blended. As the binder, polystyrene, which is an ordinary polymer material, polyvinylcarbazole, which is known as a polymer carrier transport material, MEH-PPV (polyphenylene vinylene), etc., are used alone or in combination of two or more. It is done. As described above, when the DAE layer contains other components, if the DAE ratio in the formed DAE layer is excessively small, the intended purpose of the present invention cannot be achieved. The ratio is usually 5% by weight or more.

(Film formation method)
There is no restriction | limiting in particular as the film-forming method of the DAE layer concerning this invention, Dry processes, such as a vacuum evaporation method and sputtering method, are employable.

(Film thickness)
The film thickness of the DAE layer according to the present invention is not particularly limited, and as shown in the examples described later, patterning according to the present invention is possible even when the thickness is about 1 nm corresponding to a monomolecular layer. If the layer is too thin, the DAE molecule cannot form a layer covering the whole, and the underlying layer is exposed locally, so that the electrode material adheres to this portion. 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 an undesired property of DAE, for example, a material having a low carrier transport ability and a low glass transition point, resulting in an increase in operating voltage and a deterioration in durability against high temperatures. Therefore, the thickness is usually 100 nm or less, preferably 50 nm or less, and particularly preferably 10 nm or less. However, when the DAE itself has excellent carrier transportability and a high glass transition point, there is no upper limit of such a film thickness.

<Intermediate layer>
(component)
The material of the intermediate layer is not particularly limited as long as it does not interfere with the characteristics of DAE and has carrier transport properties, and its purpose of formation, that is, protection of the DAE underlayer, shape retention, luminous efficiency improvement, etc. It is selected according to the purpose of formation. For example, metal films with low corrosive properties such as Ag, Au, Pt, inorganic materials such as ITO, Alq3 (aluminato-tris-8-hydroxyquinolate), α-NPB (N, N-di (naphthalene-1-yl) -N , N-diphenyl-benzidene), organic molecular materials such as carrier transport materials such as triphenylamine, polymer materials such as polystyrene and polyvinyl carbazole known as polymer carrier transport materials, and MEH-PPV (polyphenylene vinylene). It is done. Among these, a carrier transport material is preferably used for the purpose of improving luminous efficiency. In addition, the material of an intermediate | middle layer can use said 1 type individually or in mixture of 2 or more types. The intermediate layer may be formed by laminating two or more layers made of the above materials. When two or more intermediate layers are laminated, the film thickness of the intermediate layer described later refers to the total film thickness thereof.

(Film formation method)
There is no restriction | limiting in particular as the film-forming method of the intermediate | middle layer which concerns on this invention, Dry processes, such as a vacuum evaporation method and sputtering method, are employable.

(Film thickness)
The film thickness of the intermediate layer depends on the thickness of the DAE layer. For example, in the case of an ultrathin film having a DAE of 1 nm, the patterning effect by DAE isomerization is maintained if the intermediate layer is about 1 nm. The thicker the DAE layer, the thicker the intermediate layer. When the thickness of the intermediate layer is significantly thicker than that of the DAE layer, for example, when the intermediate layer is more than twice as thick as the DAE layer, the effects of the DAE layer, that is, the ring-opening state and the ring-closing state due to isomerization, The patterning property due to the difference in the adhesion of the electrode material due to the difference in the above is impaired. Moreover, regardless of the thickness of the DAE layer, when the thickness of the intermediate layer exceeds 20 nm, the effect of the DAE layer disappears.
Therefore, the thickness of the intermediate layer is preferably in the range of 1 to 20 nm and not more than twice the thickness of the DAE layer, particularly about 0.5 to 1 times.

[Method of manufacturing organic electronic device]
Below, the manufacturing method of the organic electronic device of this invention is demonstrated according to the operation procedure.

In the following, a first electrode is formed on a substrate according to a conventional method, an organic layer is formed thereon, and a DAE layer and an intermediate layer are formed for patterning the second electrode formed on the organic layer. The method of the present invention will be described by exemplifying the case of forming and forming the second electrode in a predetermined pattern shape, but the present invention is not limited to this method,
(1) A DAE layer is formed on a substrate, an isomerization pattern is formed on this DAE layer, an intermediate layer is formed, a first electrode is formed following this pattern, and an organic layer and a second electrode are further formed. How to form
(2) In the method of (1) above, the second electrode is also formed by forming an DAE layer and an intermediate layer on the organic layer and patterning by forming an isomerization pattern of the DAE layer, as will be described later.
(3) A DAE layer and an intermediate layer are 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 patterned by forming an isomerization pattern of the DAE layer. Electrode patterning can be performed in a variety of ways, including methods. In any case, as described above, the intermediate layer may be formed on the DAE layer after forming the isomerization pattern of the DAE layer, or after the intermediate layer is formed on the DAE layer, the isomerization of the DAE layer may be performed. A formation pattern may be formed.

<Patterning of second electrode>
[1] A first electrode is formed on a substrate according to a conventional method.

[2] A predetermined organic layer is formed on the first electrode according to a conventional method.

[3] An underlayer containing the above-described DAE is formed.
Here, the underlayer is preferably formed by a vacuum deposition method, a sputtering method, or the like. However, in the case of forming by a doctor blade method, a cast method, a spin coating method, a dipping method, or the like, DAE is diluted with a solvent and a coating solution It is desirable to prepare 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.
As described above, the underlayer containing DAE is usually formed to a thickness of 1 nm or more, preferably 2 nm or more, and usually 100 nm or less, preferably 50 nm or less, particularly 10 nm or less.

[4] DAE in the underlayer is caused to undergo an isomerization reaction in a predetermined pattern.
As a method for causing this isomerization reaction, a method using light irradiation is preferable because it is simple and patterning accuracy is high. 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 a closed ring state to a ring-opened state.
Therefore, using this property, it is preferable to cause isomerization of DAE in a predetermined pattern in the underlayer, for example, as in (A) or (B) below.

  (A) The underlayer containing DAE is entirely irradiated with ultraviolet light in a wavelength region of 300 to 430 nm, particularly 300 to 400 nm, 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 to isomerize the DAE at the irradiated portion from the closed state to the open state. This forms an underlayer in which the DAE ring-opened molecules exist in a predetermined pattern shape in the matrix of the DAE ring-closed molecules. In addition, when all the underlayers are in a ring-closed state, the first entire surface irradiation process can be omitted.

  (B) The base layer containing DAE is entirely irradiated with light in the wavelength region of 450 to 600 nm, particularly 500 to 600 nm, so that the DAE of the base layer is fully opened. Thereafter, ultraviolet light of 300 to 430 nm, particularly 300 to 400 nm, is irradiated to a predetermined pattern by laser spot scanning to isomerize the DAE in the irradiated portion from the ring-opened state to the ring-closed 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. In addition, when all the underlayers are in the ring-opened state, the first entire surface irradiation step can be omitted.

[5] An intermediate layer is formed on the underlayer containing DAE.
This intermediate layer is preferably formed by a vacuum deposition method, a sputtering method, or the like. However, when forming by a doctor blade method, a cast method, a spin coating method, a dipping method, etc., the intermediate layer material is diluted with a solvent to form a coating solution. It is desirable to prepare and use this coating solution. In this case, the type of solvent is not particularly limited as long as it does not attack the DAE layer.
As described above, the intermediate layer is formed in a thickness of 1 to 20 nm in a thickness of 2 times or less, preferably about 0.5 to 1 times the thickness of the DAE underlayer.
The process [4] and the process [5] can be interchanged.

[6] As described above, the second electrode is formed on the intermediate layer on the underlayer subjected to the DAE isomerization reaction according to a predetermined pattern.
This second electrode is preferably formed by a vacuum deposition method.
Although there is no restriction | limiting in particular as a constituent material of a 2nd electrode, What produces a difference in adhesiveness by isomerization of DAE is used preferably, for example, 1 type, or 2 or more types of metals, such as magnesium, aluminum, calcium, and lithium Is mentioned.

  There is no restriction | limiting in particular in the film thickness of this 2nd electrode, Although it should just be a grade which can fully exhibit the electrode performance requested | required in the use of the said organic electronic device, Usually, it is 50 nm or more and 100 nm or less.

  By depositing an electrode material on the intermediate layer on the underlayer on which the isomerization pattern is formed in this way, the electrode material is selectively formed on the intermediate layer corresponding to the portion where the DAE of the underlayer is in a closed state. Since the electrode material does not adhere to the portion where DAE is attached and the DAE is in an open state, the second electrode can be formed in a predetermined pattern.

  That is, in the case where DAE ring-opened molecules are formed in a predetermined pattern by laser spot scanning by the method (A) described above, this predetermined pattern portion becomes an undeposited portion of the electrode material, and other matrix portions Second electrode is formed. 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, this predetermined pattern portion becomes a vapor deposition portion of the electrode material, and this portion is the second electrode. Is formed.

  According to such a method of the present invention, it is possible to pattern an extremely fine electrode having a width of 450 nm or less, for example, 260 to 450 nm, with high accuracy. That is, in general, the spot of the laser beam can be narrowed down 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.

  On the other hand, in the DAE, the electrode material does not adhere in the ring-opened state, and the electrode material adheres in the closed-ring state. Even if it is not in a state, the electrode material adheres even if, for example, 50% or more is in a closed state, depending on the type of DAE. Therefore, for example, the spot diameter of the laser beam, including the part that was closed by direct laser irradiation and the part that was partially closed by the influence of the laser beam in the vicinity. 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 in 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 on the intermediate layer of this portion.

In addition, said light irradiation is not restricted to the thing by scanning of a laser spot, A light shielding mask may be used and a mask and spot scanning may be used together.
In the present invention, the patterning of the electrodes is not limited to the method using only the DAE isomerization as described above, but by using another patterning means such as a metal mask separately, further highly accurate and efficient patterning. It is also possible to perform.

  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.

  Hereinafter, the present invention will be described in more detail with reference to experimental examples, examples and comparative examples.

Experimental example 1
A DAE thin film having a film thickness of 100 nm was formed on a slide glass substrate by vacuum evaporation using DAE represented by the following structural formula.

Next, the DAE thin film was irradiated with ultraviolet light having a wavelength of 365 nm while partially changing the irradiation amount to form a 5-stage isomerization state on the same DAE thin film. That is,
State 0 = all DAE molecules are in the open state State 1 = about 20% of all DAE molecules are in the closed state (about 80% are in the open state)
State 2 = about 50% of all DAE molecules are in a closed state State 3 = about 80% of all DAE molecules are in a closed state State 4 = almost 100% of all DAE molecules are in a closed state. At this time, since the DAE is colored by being in a ring-closed state, the DAE thin film is partially colored depending on the degree of isomerization.

Next, magnesium was vacuum-deposited on the DAE thin film to a thickness of 100 nm to examine the adhesion state of magnesium.
As a result, as shown in FIG. 1, when the ring-closing molecule was 50% or less (states 1 and 2), no magnesium was observed, but when it was 80% or more (states 3 and 4), magnesium was found to adhere. It was.
FIG. 1 also shows an absorption spectrum in each state for examining the ratio of the ring-closed molecules.

Experimental example 2
In Experiment 1, an experiment for examining the adhesion state of magnesium was performed in the same manner except that the DAE represented by the following structural formula was used.

  As a result, this DAE also exhibits magnesium adhesion in the ring-closed state and non-adhesion of magnesium in the ring-opened state, but the degree is different from the DAE used in Experimental Example 1, and the ring-closed molecules account for 50% of all molecules. Even magnesium adhered.

  From these results, it can be seen that DAE shows selective adhesion of magnesium depending on its isomerization state, but the ratio of the ring-closed bodies showing magnesium adhesion is not absolute and varies depending on individual DAE.

Experimental example 3
Experiments for adhesion of magnesium to the Alq3 layer on the DAE thin film were performed according to the procedure shown in FIGS. First, a DAE thin film 2 having a film thickness of 15 nm was formed on a glass substrate 1 in the same manner as in Experimental Example 1 (FIG. 2A).

  The DAE thin film 2 is entirely irradiated with ultraviolet light 3 having a wavelength of 365 nm to form a colored state (closed state) (FIG. 2B), and then a red laser (power 1 mW) 4 having a wavelength of 650 nm is about 1 mm in diameter The required number of samples (one with the ring-opened molecule spot formed in the ring-closed molecule) were produced by irradiating with the spot (1) to erase the color (FIG. 2 (c)).

Further, Alq3 was vapor-deposited on the DAE layer of each sample with the following film thickness (however, Alq3 was not vapor-deposited in No. 1) (FIG. 2 (d)). Similarly, magnesium was vapor-deposited (FIG. 2 (e)), the adhesion state of magnesium was examined, and the result is shown in FIG.
No.1: Alq3 film thickness 0nm
No.2: Alq3 film thickness 5nm
No.3: Alq3 film thickness 10nm
No. 4: Alq3 film thickness of 20 nm

From FIG. 3, in No. 1 to 3, there is a non-attached portion of magnesium in the portion corresponding to the ring-opening molecule of DAE (decolored portion), but in No. 4, there is no unattached portion.
From this result, the relationship between the film thickness of Alq3 and the adhesion of magnesium was examined in detail. As a result, the film thickness of the Alq3 intermediate layer was about 15 nm, which is equal to the film thickness of the DAE layer. When the film thickness of the Alq3 intermediate layer exceeds 15 nm, the selective adhesion of magnesium due to DAE isomerization is impaired.

Experimental Example 4
In Experimental Example 3, similar samples were prepared by changing the film thickness of the DAE layer and the film thickness of the Alq3 intermediate layer. Similarly, the presence or absence of selective adhesion of magnesium was examined, and the results are shown in Table 1. .

  From Table 1, even if the thickness of the Alq3 intermediate layer is increased up to about the thickness of the DAE layer, selective adhesion of magnesium appears, but if the thickness of the Alq3 layer exceeds 20 nm, no matter how thick the DAE layer is It can be seen that such selectivity does not occur on the Alq3 layer surface. Therefore, when Alq3 is used as the intermediate layer, the film thickness is desirably 20 nm or less.

  Alq3 is a typical electron transport material, but when an experiment using α-NPB as an intermediate layer material was further performed, the same result as in the case of Alq3 was obtained. Similar results were obtained when silver was used as the intermediate layer material.

Example 1
A magnesium cathode was formed by applying the present invention to an organic EL element which is a typical organic electronic device.

A copper phthalocyanine layer as a hole injection layer is formed on the ITO substrate by vapor deposition to a thickness of 2 nm, an α-NPB layer is formed as a hole transport layer by vapor deposition at a thickness of 30 nm, and a rubrene as a light emitting layer is further formed thereon. Α-NPB doped with is formed by vapor deposition with a film thickness of 20 nm. Furthermore, the DAE thin film used in Experimental Example 1 was deposited thereon to a thickness of 5 nm to form a DAE thin film. Thereafter, in the same manner as in Experimental Example 3, the DAE thin film was irradiated with ultraviolet light for 10 minutes to make the DAE layer closed, and then a ring-opened pattern with a width of 15 μm was formed by spot scanning with a red laser having a wavelength of 650 nm. It was formed in a straight line shape and a zigzag shape. Then, Alq3 was formed by vapor deposition with a film thickness of 5 nm as an intermediate layer (electron transport layer), and magnesium was further vacuum-deposited with a thickness of 100 nm.
When this magnesium deposited film was observed with a microscope, a magnesium undeposited pattern corresponding to a pattern obtained by isomerizing DAE by scanning with a laser was formed on the Alq3 layer, and magnesium was deposited on the other portions. Was confirmed.

  Next, using the ITO substrate as the anode and the formed magnesium deposited film as the cathode, voltage was applied between the two electrodes to inject current, and the state of light emission was observed from the ITO side, corresponding to the red laser scanning pattern. Thus, it was confirmed that a non-light-emitting pattern was formed, and the portion where magnesium was formed emitted light brightly.

Comparative Example 1
An organic EL device was produced in the same manner as in Example 1 except that the Alq3 intermediate layer was not formed. At this time, magnesium was deposited with the same selective adhesion as in Example 1.
When an electric current was applied to the organic EL device in the same manner, a light-emitting portion corresponding to the isomerization reaction pattern of DAE was visually confirmed, but the light in the light-emitting portion was extremely dark.
This is because, in Example 1, the Alq3 layer inserted as an intermediate layer effectively functions as an electron transport layer, and thus efficient light emission was performed, whereas in Comparative Example 1, there was no Alq3 intermediate layer. Therefore, it was estimated that the light emission efficiency was inferior.

Comparative Example 2
An organic EL device was produced in the same manner as in Example 1 except that the DAE layer was not formed. At this time, magnesium adhered to the entire surface.
When current injection was similarly performed on this organic EL element, it emitted bright light, but it was not possible to confirm that the entire surface emitted light and some pattern was formed.

In the above embodiment, the magnesium non-adhered pattern is formed by red laser scanning, but a colored (isomerization from ring-opened body to ring-closed body) line is formed by scanning with an ultraviolet laser, and the shape follows this scanning pattern. It was also possible to pattern the electrodes of the organic EL element in the same manner using the magnesium adhesion pattern.
Further, the same result could be obtained even when the isomerization pattern of the DAE layer was formed after the formation of the Alq3 intermediate layer.

  Further, the present invention is not limited to organic EL devices, and is obviously applicable to various organic electronic devices such as organic TFTs and organic memory elements. It is also clear that the DAE used can be similarly applied to those other than the examples given here.

FIG. 1 (a) is a photograph showing the isomerization state of DAE and the adhesion state of magnesium in Experimental Example 1, and FIG. 1 (b) is an absorption spectrum showing the ring-closing molecular ratio of the same DEA. It is explanatory drawing which shows the experimental method in Experimental example 3. FIG. It is a photograph which shows the adhesion state of magnesium in Experimental example 3.

Explanation of symbols

1 Substrate 2 DAE thin film 3 Ultraviolet light 4 Red laser 5 Isomerization pattern 6 Alq3 layer

Claims (4)

In 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 / or between the second electrode and the organic layer. In addition,
An organic electronic device having a layer containing 1,2-diarylethene which may have a substituent for patterning an electrode by using a difference in adhesion of an electrode material ,
The layer containing 1,2-diarylethene which may have a substituent forms a pattern with different isomerization states of 1,2-diarylethene which may have a substituent corresponding to the electrode pattern by light irradiation. Is a layer in which electrode patterning is performed due to the difference in adhesion with the electrode material due to the difference in isomerization,
Organic having a carrier transporting intermediate layer between the first electrode and the layer containing 1,2-diarylethene and / or between the second electrode and the layer containing 1,2-diarylethene Electronic devices. In 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 layer. Any one or more
An organic electronic device having a layer containing 1,2-diarylethene which may have a substituent for patterning an electrode by using a difference in adhesion of an electrode material ,
The layer containing 1,2-diarylethene which may have a substituent forms a pattern with different isomerization states of 1,2-diarylethene which may have a substituent corresponding to the electrode pattern by light irradiation. Is a layer in which electrode patterning is performed due to the difference in adhesion with the electrode material due to the difference in isomerization,
Organic having a carrier transporting intermediate layer between the first electrode and the layer containing 1,2-diarylethene and / or between the second electrode and the layer containing 1,2-diarylethene Electronic devices.   3. The organic electronic device according to claim 1, wherein the first electrode and / or the second electrode includes patterns corresponding to patterns having different isomerization states of the layer containing the 1,2-diarylethene. And organic electronic devices. In a method for producing an organic electronic device that functions by applying a voltage to a layer made of an organic electronic material, the adhesion with an electrode material differs depending on the isomerization, and may have a substituent, which may have a substituent. A step of forming an undercoat layer, a step of subjecting 1,2-diarylethene of the undercoat layer to an isomerization reaction in a predetermined pattern, a step of forming a carrier transporting intermediate layer on the undercoat layer, and the intermediate layer And a step of forming an electrode pattern corresponding to the predetermined pattern by applying an electrode material on the layer.

Images