JP2002231448A - Conductive element, organic electroluminescence element and method of manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture an organic EL element of a high definition multicolor display having a light emitting layer of different light emitting colors on the same substrate by a simple method. SOLUTION: An electrode 2 is formed on the substrate 1. A positively electrifying electrification layer 3 is formed by selectively imparting a liquid electrifying material to a desired position by an ink jet method. The substrate is soaked in an electrolyte 4, and an organic compound becoming an anion in the electrolyte 4 is sucked in the electrification layer 3 to form an organic compound layer 5. Next, the substrate is soaked in an electrolyte 6, an organic compount becoming a cation in the electrolyte 6 is sucked in the organic compound layer 5, an organic compound layer 8 is formed by strictly controlling the film thickness by repeating the operation, and an electrode 9 is formed on this organic compound layer 8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device used for a flat panel display, a projection display, a printer, and the like, a conductive element which is a constituent member of the device, and a method of manufacturing these devices.

[0002]

2. Description of the Related Art As an organic electroluminescence device (hereinafter referred to as "organic EL device"), a carrier injection type EL device using an organic solid such as anthracene single crystal was studied in detail in the 1960s. These devices were of a single-layer type, and thereafter, Tang et al. Proposed a stacked organic EL device having a light emitting layer and a hole transport layer between a hole injection electrode and an electron injection electrode. . The light emission mechanism of these injection type EL devices includes electron injection from the cathode and hole injection from the anode, movement of electrons and holes in a solid,
They are common in that they undergo recombination of electrons and holes and light emission from the generated singlet excitons.

As a typical example of a laminated organic EL device, an ITO (indium tin oxide) film is formed on a glass substrate as an anode, and a TPD (N, N'-diphenyl) represented by the following structural formula is formed thereon. -N, N'-di (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine) is formed at a thickness of about 50 nm, and Alq3 (tris-tris) represented by the following structural formula is formed thereon. (8-Quinollarit) aluminum) is formed with a thickness of about 50 nm, and an element is formed by vapor-depositing an Al.Li alloy as a cathode.

[0004]

[Outside 1]

The work function of ITO used for the anode is 4.4 to
By setting it to 5.0 eV, holes are easily injected into the TPD, and a metal having a work function as small as possible and stable is selected as the cathode. For example, an alloy of Al and Li or an alloy of Mg and Ag is used. According to this configuration, 5 to 10 V
Green light is obtained by the DC voltage of

Organic compounds used in ordinary EL devices (eg, TPD, α-NPD (bis [N- (1-naphthyl) -N-phenyl] benzidine), TAZ-01
(3- (4-biphenylyl) -4-phenyl-5-
(4-tert-butylphenyl) -1,2,4-triazole), Alq3, etc.), it is necessary to apply a high electric field of about 10 V / 100 nm to the organic compound layer-electrode junction interface in order to obtain a current amount. there were.

Further, the organic EL device can be constituted by using a polymer material. The polymer material which can be used for the organic EL device generally has conductivity and has unsaturated bonds in the molecular structure. It is known that a compound having such a compound exhibits good characteristics. Examples of such a polymer material include the following compounds.

(1) PPV (polyphenylenevinylene) (2) PPP (polyparaphenylene) (3) PVK (polyvinylcarbazole) (4) PDAF (polydialkylfluorene) (described in US Pat. No. 5,900,327) The above PPP The structure of is shown below.

[0009]

[Outside 2]

[0010]

When a full-color display element is formed by combining a plurality of luminescent colors in an organic EL element, luminescent layers made of different types of luminescent materials are selectively formed on the same substrate. There is a need to.

In a conventional process of forming a light emitting layer using a low molecular material, different types of low molecular materials are selectively vacuum-deposited by a mask shielding method.
It was difficult to obtain a high-resolution resolution of about 00 dpi. In addition, when a light emitting layer is formed using a conventional polymer material, a method of forming a film by synthesizing a precursor of a polymer material on a substrate cannot be used because a vacuum evaporation method cannot be used. Thus, forming a high-resolution light-emitting layer was more difficult than a low-molecular material. For this reason, there has been a limit in achieving higher definition in the full color organic EL device.

As one means for solving such a problem,
A patterning method using an ink jet method has been proposed (JP-A-10-12377).

In this method, a liquid light emitting material is applied to a desired region on a substrate using an ink jet printer, so that R (red), G (green), and B (blue) light emitting layers are selectively formed. It can be formed by two-dimensional arrangement.

However, in the ink-jet method, since the liquid light-emitting material is disposed on the substrate, the obtained light-emitting layer forms a convex shape having a central portion having a maximum thickness, and a film having a Gaussian thickness from 0 to the maximum thickness. This results in a thickness distribution. As a means for eliminating such a film thickness distribution, there is a method in which a partition is formed on a substrate and a light emitting material is applied to a concave portion surrounded by the partition. However, even when such a partition is used, it can be obtained. The thickness of the light emitting layer has a distribution of 10% or more. The light emitting layer having a film thickness distribution produces a distribution of the applied electric field strength,
It has been found that a voltage threshold at which light emission starts varies from place to place, which is a factor that causes luminance unevenness in one pixel and in the entire display element.

On the other hand, M. F. Rubner et al. (Adv. Mater. 1998, 10, No. 17, p. 145).
According to 2), P which is a blue light emitting material as an organic EL is used.
For PP (Poly (p-phenylen)), it is disclosed that a water-soluble derivative of a polyanion and a polycation is made to form a laminated film, according to which a prepared substrate is treated with an anionic PPP solution and a cationic PPP. The light-emitting layer is formed by sequentially placing the ionic film into a solution and laminating a film having an opposite charge on the ionic film adsorbed first in the next step. This shows that the desired film thickness can be easily and accurately obtained by the number of lamination steps because the film thickness to be formed is substantially constant.

However, in this method, it is difficult to form a light-emitting layer selectively and accurately at a specific position of a display element having a large number of pixels. It will be an indispensable technology in creating.

An object of the present invention is to solve the above problems and to provide a conductive element in which different kinds of organic compound layers are selectively and uniformly formed on the same substrate with a uniform film thickness. In particular, it is an object of the present invention to provide a high-resolution, full-color display organic EL device having light-emitting layers of different emission colors with a uniform film thickness at a low price by a simple manufacturing method. is there.

[0018]

A feature of the present invention is that a charged region having a positive or negative charge is formed at a predetermined position on a substrate, and an organic compound is immersed in an electrolytic solution in which an organic compound is ion-dissociated. In this case, the organic compound is deposited only in a specific region.

Further, the step of forming a charged region in a specific region is characterized in that a solution of a charged material is applied to a specific position by using an ink jet method.

More specifically, the charging material is first applied to a specific position on the substrate, and then the substrate is immersed in an electrolytic solution in which the organic compound is ion-dissociated, and the coating is applied first. And adsorbing and depositing the organic compound ions on the charged charging material to form an organic compound layer.

In a preferred embodiment of the conductive element of the present invention, the charging material comprises an electrolyte, and the electrolyte has a silanol group and an ion-dissociative functional group.

A second aspect of the present invention is an organic electroluminescent device using the conductive element of the present invention, wherein the organic compound layer of the element is formed of a light emitting material.

Further, a third aspect of the present invention is a step of applying a charging material on a first electrode disposed on a substrate, and immersing the substrate in an electrolytic solution containing organic compound ions to form a coating on the charging material. And a step of forming an organic compound layer by adsorbing organic compound ions on the organic compound layer, and a step of forming a second electrode on the organic compound layer.

In the method of manufacturing a conductive element according to the present invention, the step of forming the organic compound layer includes immersing the substrate alternately in an electrolyte containing an organic compound cation and an electrolyte containing an organic compound anion. Or alternately laminating each organic compound layer, or repeating the step of forming the charged layer and the step of forming the organic compound layer by changing the type of the organic compound used, to form a plurality of layers on the same substrate. The formation of a kind of organic compound layer is included as a preferred embodiment.

Further, a fourth aspect of the present invention is to form a film thickness of an organic compound layer with high accuracy by using the above-mentioned manufacturing method. An object of the present invention is to provide a method for manufacturing an organic electroluminescence device having uniform light emission characteristics by eliminating voltage variations.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention forms a film whose surface is positively or negatively charged (hereinafter referred to as a charged layer) at an arbitrary position on a substrate, and dissociates ions having the opposite polarity thereat. The organic compound is adsorbed to selectively form an organic compound layer at a specific position on the substrate.

That is, a charged layer is previously formed on a substrate, and the substrate is immersed in an electrolyte solution of the organic compound ionized to the opposite polarity to that of the charged layer, whereby the organic compound ions are transferred to the charged layer on the substrate. Is characterized in that it is adsorbed on to form an organic compound.

It is also possible to increase the film thickness by adsorbing organic compound ions of which polarity is changed alternately and sequentially and repeating the number of times.

Particularly, in the present invention, the most characteristic feature is that the charged layer is applied to a desired position by an ink jet method. Since the charging layer according to the present invention is a member used only for the adsorption of organic compound ions, it is sufficient that the charging property can be imparted to a desired position on the insulating substrate.
It suffices if a small amount of a liquid charging material can be applied by an ink jet method so that the charging property can be substantially provided. When viewed as a conductive element, it is necessary to flow an electric current, so that the thickness of the charging layer needs to be thin, and it is desirable that the charging layer is substantially a monolayer.

Furthermore, an electrolyte solution of an anionized organic compound and an electrolyte solution of a cationized organic compound are used in combination, and the insulating substrates are alternately immersed to alternately laminate the respective organic compound layers one by one. Therefore, the thickness of the organic compound layer can be controlled at the molecular level.
At the same time, a uniform film thickness can be obtained over a wide area.

In the present invention, the formation of the charged layer and the step of forming the organic compound layer on the charged layer are repeated by changing the kind of the organic compound to form a laminated film of different kinds of organic compound layers. Can be.

Hereinafter, the present invention will be described in detail with reference to the drawings.

FIG. 1 is a schematic view showing the steps of a method for manufacturing a simple matrix type conductive element according to the present invention. In the figure, 1 is a substrate, 2 and 9 are electrodes, 3 is a charged layer, 4 and 6 are electrolytes containing organic compound ions, and 5, 7, and 8 are organic compound layers. Also, (a-2) to (d-2) on the right side of the paper are AB of the respective substrates (a-1) to (d-1) on the left side of the paper.
It is sectional drawing. Hereinafter, each step will be described.

Step (a) A stripe-shaped electrode 2 is formed on a substrate 1. Substrate 1
The material is not particularly limited, but is preferably a material that is not affected when immersed in the electrolytes 4 and 6 described below.
When an organic EL element is formed and light emission is observed from the substrate side, a transparent substrate such as glass or plastic is used. However, when light emission is observed from the opposite side, an opaque substrate may be used. .

The electrode 2 is preferably made of a conductive material generally used for an electrode configuration of a device.
TO, indium oxide, tin oxide, Cd ₂ SnO ₄ , zinc oxide, copper iodide, gold, platinum, and the like. The cathode is an alkali metal, an alkaline earth metal, or an alloy thereof such as sodium, potassium, magnesium, and lithium. , Sodium-potassium alloy, magnesium-indium alloy, magnesium-silver alloy, aluminum, aluminum-lithium alloy, aluminum-copper alloy, aluminum-copper-silicon alloy. When an organic EL element is formed and light emission is observed from the substrate side, a transparent conductive material such as ITO is used for the electrode 2.

Further, a charging layer 3 is formed in a desired region on the electrode 2 on the substrate 1 (a-1, a-2). In the present invention, preferably, a liquid charging material is applied onto the electrode 2 by an ink jet method and dried to form the charging layer 3.

In this embodiment, an example in which the positively charged layer 3 is formed will be described.

The conductive material preferably used in the present invention is not particularly limited as long as it shows a positive or negative chargeability in the electrolytic solution 4. However, when the charge layer 3 is formed by an ink jet method, Since the material is provided on the substrate 1 in a liquid state, the material needs to be a material that can be dissolved or dispersed in the liquid. Further, the charged material needs to be fixed to the electrode 2 so as not to be dissolved in the electrolytic solution 4 when immersed in the electrolytic solution 4 in a later step. Therefore, it is preferably an electrolyte, and particularly, a compound having a silanol group and an ion-dissociating functional group for bonding to the electrode 2 is preferable. Further, the length is desirably as thin as possible so as not to impair the conductivity of the element, and is desirably as short as about 1 to 10 carbon atoms, preferably about 1 to 5 carbon atoms. Since the molecular length of the compound forming the charged layer 3 affects the supply of carriers such as electrons and holes from the electrode 2 to the organic compound layer, the molecular length of the compound is to obtain a film thickness enough to allow tunnel current to flow. It is particularly desirable that the thickness be 2 nm or less, preferably 0.15 to 1 nm. Specific examples of the charging material include those having the following structures.

[0039]

[Outside 3]

Further, the following general silane coupling agents can also be used.

Whether the charged material is positively charged or negatively charged is determined by the polarity of the group bonded to Si.
In the case of cyclic amines, the charge is positive, and in the case of sulfonic acid groups, the charge is negative.

[0042]

[Outside 4]

Although a compound having a silanol group has been exemplified here, it is also possible to use a titanium-based coupling agent. In any of the materials, the hydrogen of the hydroxyl group is released, and the material is chemically bonded to silicon atoms, iridium atoms, and the like forming the substrate, and can be firmly adhered.

When the charging material is applied on the electrode 2 by an ink-jet method, the solution used is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight.
It is preferably used as a weight percent aqueous solution. Further, methanol or the like may be appropriately added for controlling the drying property after the application. After simple drying, the substrate is washed with pure water in order to wash away the unreacted charged material. Further, if necessary, the substrate is heated, heated in a vacuum, or the like, and dried. In this way, a required amount of charged material can be arranged on the substrate. In this example, an example is shown in which a cationic charging layer having a positive charge is formed by the above method.

Step (b) The substrate 1 having the charged layer 3 formed at a predetermined position is immersed in an electrolytic solution 4 of an ionic organic compound having a polarity opposite to the polarity of the charged layer (b- 1). The organic compound used in the present invention is an electrolyte to which an ionic group is added. The organic compound is ion-dissociated in the electrolytic solution 4 and becomes a cation or an anion depending on the added ionic group. Since the polarity of the organic compound ions is opposite to the polarity of the charged layer 3 (anion in this example), the organic compound ions in the electrolytic solution 4 are adsorbed on the surface of the charged layer 2 to form the organic compound layer 5. (B-2).

The organic compound used in the present invention includes:
A low-molecular material or a high-molecular material can be preferably used as long as it can add an ionic group. For example, when forming an organic EL element and forming a light emitting layer using a light emitting material as an organic compound, PPV, PPP, PVK, P
A polymer material in which an ion dissociable side chain is introduced into DAF is preferably used. The structure in which the side chain is introduced into PPP is shown below. Such compounds are disclosed in the aforementioned references by Rubner et al.

[0047]

[Outside 5]

The following compounds can also be used as examples of other ionic organic compounds. Here PP
V (polyphenylene vinylene) and PT (polythienyl)
An example was shown. A positively chargeable group and a negatively chargeable group are prepared to impart polarity when ionized, and are bonded to a monomer and then polymerized to form an ionic group in the same manner as in the previous example. The resulting polycation or polyanionic high molecular organic compound is obtained.

Alternatively, a polymer compound may be prepared in advance, and the above-mentioned positively chargeable group and negatively chargeable group may be added later.

[0050]

[Outside 6]

(Structure of PPV) (Structure of PT) As the solvent for the electrolytes 4 and 6, general water is used, but any solvent that can dissociate ions can be used. May be included.

In this example, an example was shown in which the anionic organic compound layer was adsorbed because the previously applied charging layer was cationic.

Step (c) The substrate 1 on which the organic compound layer 5 is formed is immersed in the cationized organic compound electrolyte 6 (c-1). Since the surface of the organic compound layer 5 is anionized, the cationized organic compound in the electrolytic solution 6 is not anionic.
The organic compound layer 7 is adsorbed on the surface to form a new organic compound layer 7 (c-2).

This step can be ended here. By repeating the steps (b) and (c), the anionized organic compound layer 5 and the cationized organic compound layer 7 are separated one by one. They can be alternately stacked. The thickness of the organic compound layer 8 finally obtained can be controlled on a molecular level by the number of steps.

The organic compound used here is obtained by giving anions and cations of different polarities to the same material, but by giving polar groups to completely different types of compounds to form a laminated film of different compounds. Is also possible.

Step (d) Thereafter, in order to eliminate the cationic groups remaining on the surface, the surface is immersed in a 1% acetic acid solution as a neutralizing treatment.

Further, after the substrate was dried, opposing stripe electrodes 9 were formed on the organic compound layer 8 to form d-1 and d- electrodes.
2) Obtain the conductive element of the present invention. The electrode material is the same as the electrode 2 described above, and is appropriately selected depending on the settings of the cathode and the anode.

The shape of the electrodes 2 and 9 is not particularly limited as long as a voltage can be applied while sandwiching the organic compound layer 8.
A stripe shape or the like is appropriately selected according to a device configured using the conductive element of the present invention.

In the case of forming a simple matrix driven organic EL element, the organic EL element may be formed in a stripe shape orthogonal to each other and an organic compound layer 8 (light emitting layer) is formed at the intersection thereof. In the case of the above, a switching element such as a TFT (thin film transistor) is disposed on each pixel electrode using the electrode 2 as a pixel electrode, and an organic compound layer 8 (light emitting layer) is formed on the pixel electrode.
And the electrode 9 may be a common electrode.

When forming different types of organic compound layers 8, for example, when forming a light emitting layer of an organic EL element for full color display, it is necessary to form light emitting elements of three colors of red, green and blue. . In this case, the steps (a) to (c) are defined as one cycle, and a plurality of cycles are performed while changing the type of the organic compound to be used, thereby selectively forming different types of organic compound layers 8 at desired positions. Can be. In this case, the outermost organic compound layer is subjected to a neutralization treatment or the like (oxidation treatment for cations, reduction treatment for anions), and no new organic compound ions are adsorbed thereon in the next cycle. You need to do that.

Further, when an organic EL device is formed, a hole transport layer or an electron transport layer which works together with the organic compound layer 8 is formed between the electrode 2 and the electrode 9 by a vacuum deposition method or the like. May be. In this case, for example, a hole transport layer is first formed on the electrode 2, and then the charging layer 3 is formed by an inkjet method. When an electron transport layer is formed on the organic compound layer 8, it is necessary to form the electron transport layer material by vapor deposition or the like after performing the above-described neutralization treatment.

As the material for the hole transport layer used in the organic EL device of the present invention, specifically, the following compounds are preferably used. α-NPD (shown by the following structural formula)

[Outside 7]

1-TANTA: 4,4 ', 4 "-tris (1-naphthylphenylamino) triphenylamine 2-TANTA: 4,4', 4" -Tris (2-naphthylphenylamino) triphenylamine TCTA : 4,4 ', 4 "-tris (N-carbazoyl) triphenylamine p-DPA-TDAB: 1,3,5-tris [N- (4
-Diphenylaminophenyl) phenylamino] benzene TDAB: 1,3,5-tris (diphenylamino) benzene TDTA: 4,4 ', 4 "-tris (diphenylamino) triphenylamine TDAPB: 1,3,5-tris [(Diphenylamino) phenyl] benzene Examples of the electron transporting material used in the organic EL device of the present invention include the following compounds in addition to Alq3 described above: BeBq: bis (benzoquinolinolato) beryllium Complex DTVBi: 4,4'-bis- (2,2-di-p-tolyl-vinyl) -biphenyl Eu (DBM) 3 (Phen): tris (1,3-diphenyl-1,3-propanediono) ( Monophenanthroline) Eu (III) Diphenylethylene is also used as another hole transporting material or electron transporting material. Derivatives, triphenylamine derivatives, diaminocarbazole derivatives, bisstyryl derivatives, benzothiazole derivatives, benzoxazole derivatives, aromatic diamine derivatives, quinacridone compounds, perylene compounds, oxadiazole derivatives, coumarin compounds, anthraquinone derivatives, distyryl Arylene derivative (D
PVBi), oligothiophene derivative (BMA-3T)
And the like. These materials are preferably laminated in an amorphous state by a vacuum deposition method.

Next, a description will be given of the configuration of a head which is a main part of an ink jet printer preferably used in the present invention. 2A and 2B are diagrams schematically illustrating an example of the configuration of an ink jet head. FIG. 2A is a cross-sectional view in the ink ejection direction, FIG. 2B is a cross-sectional view taken along line AB of FIG. FIG. This example is a bubble jet (registered trademark) type ink jet head using an electrothermal converter as an energy generating element. In the present invention, a piezo jet type ink jet head using a piezoelectric element is also preferably used. Can be

In FIG. 2, 10 is a substrate, 14 is a groove as an ink flow path, 15 is a heating head, 16 is a protective film, 17
a and 17b are aluminum electrodes, 18 is a heating resistor layer,
19 is a heat storage layer, 20 is a substrate, 21 is ink, 22 is an orifice, 23 is a meniscus, 24 is an ink droplet, and 25 is an electrode.

The ink jet head shown in FIG. 2 is constituted by bonding a substrate 10 made of glass, ceramic, plastic or the like having a groove 14 through which ink passes, and a heating head 15 used for thermal recording. The heating head 15 has a protective layer 16 made of silicon oxide or the like, aluminum electrodes 17a, 1
7b, a heating resistor layer 18 made of nichrome or the like, a heat storage layer 19, and a substrate 20 having good heat dissipation such as alumina. The ink 21 has a discharge orifice (micro hole) 22
And a meniscus 23 is formed by pressure. Here, when an electric signal is applied to the electrodes 17a and 17b, the area indicated by n of the heating head 15 generates heat rapidly, bubbles are generated in the ink 21 in contact with the area, and the meniscus 23 protrudes by the pressure, An ink droplet 24 is formed from the orifice 22 and pops out, and flies toward an electrode 25 which is a recording material in the present invention.

Usually, an ink jet head is used as a multi-head in which a plurality of the above-mentioned head configurations are arranged as shown in FIG.

The conductive element of the present invention is preferably applied to various devices, and in particular, an organic EL element in which an organic compound layer is formed of a light emitting material to form a light emitting layer is preferable. Also,
In addition to organic EL elements, optical sensors, photoconductors (copier drums), organic semiconductor elements (organic TFTs), temperature sensors,
It can be applied to electronic devices such as spatial modulation elements.

[0069]

(Example 1) An ITO film having a thickness of 70 nm was formed on a glass substrate having a thickness of 1.1 mm by a sputtering method, and was patterned by a conventional method to form a transparent electrode. The substrate temperature at the time of film formation was 200 ° C., the target component was 90% In and Sn
Using a 10% target and 200 scc Ar gas
m, O ₂ gas was introduced at 3 sccm to form a film by sputtering.
The work function after sputter deposition was about 4.35 eV, but this ITO film was irradiated with UV light using a low-pressure mercury lamp to increase the work function to 4.6 eV and used as an anode. The thickness was 70 nm.

The positively charged material 1 having the structure described above is
An aqueous solution containing 0.1% by weight and 5% by weight of methanol
Adjust the above transparent using an inkjet printer
Multiple drops are applied on the electrode, and the applied amount per pixel in the pixel portion is
It was about 30 picoliters. After application, bring the substrate to 80 ° C
Heat and further clean with pure water to make
The remaining unreacted charged material 1 was removed. Then the substrate temperature
2 x 10 at 80 ° C ^-2In a vacuum chamber depressurized to below Pa
Let dry. As a result, the diameter of the transparent electrode was about 0.15 mm.
Was formed.

The PPP derivative 1 having the structure shown above, and P
The electrolytic solution of PP derivative 2 (n = 10 each) is “Lan
gmuir 16, No. 11, 2000, p. 501
7-5023 "and" Adv. Mater. 1998,
10, No. 17, p. 1452 ".

The solution conditions were such that the PPP derivative 1 was an aqueous solution of 0.01 M / liter and the pH was about 4. PPP derivative 2
Has the same concentration of 0.01 M / liter,
The pH was adjusted to 4 by adding 1 M / liter.

First, the substrate on which the above-mentioned charged layer was formed was immersed in an electrolyte in which the PPP derivative 2 was anionized for 15 minutes, rinsed with water for 2 minutes, and then immersed in the electrolyte in which the PPP derivative 1 was cationized for 15 minutes. did. By repeating this operation 20 times, a PPP layer having a thickness of about 100 nm was formed.

Thereafter, as a neutralization treatment, the film was immersed in a 1% acetic acid solution for 5 minutes, and then dried in a vacuum oven at 80 ° C.

The above substrate was transferred into a vacuum chamber having a reduced pressure of 2 × 10 ⁻³ Pa or less, and a thickness of about 30 n was obtained by resistance heating evaporation.
m of Alq3 was formed into an electron transport layer. The deposition pressure was 1 × 10 ⁻³ Pa at a deposition rate of about 0.1 nm / sec.

Next, on the Alq3 layer, an Al.Li alloy was deposited as a cathode at a deposition pressure of 1 × 10 ⁻⁴ Pa for 10 nm.
Evaporation was performed, and Al was further evaporated to a thickness of 150 nm to obtain an organic EL device.

The obtained organic EL device emitted light by applying a voltage of 12 V between the anode and the cathode. Also, there was almost no threshold distribution in the light emitting region, and good light emitting threshold characteristics were exhibited.

(Example 2) An ITO film having a thickness of about 100 nm was formed as an anode on a glass substrate having a thickness of 1.1 mm by sputtering, and was patterned into a stripe pattern of 10 lines with a width of 100 µm and a gap of 40 µm.

Next, in the same manner as in Example 1, the charged material was applied to the anode at a position corresponding to the intersection between the anode and the following cathode by the ink jet method at a rate of 2 pixels per pixel.
The charged material was applied by applying 0 picoliter. Thereafter, drying was performed in the same manner as in Example 1 to form a charged layer having a diameter of about 0.1 mm. A light emitting layer composed of a PPP layer was formed thereon under the same conditions as in Example 1.

Next, when the width is 10 μm and the gap is 40 μm,
A striped cathode of lines was formed so as to be orthogonal to the anode. The cathode was formed by laminating a 10 nm-thick Al.Li alloy (Li: 1.3% by weight) and a 150 nm-thick Al under a vacuum degree of 2.66 × 10 ⁻³ Pa.

A scanning signal of +10 V pulse voltage was applied to the electrode 2 in a glove box filled with the obtained organic EL element in a nitrogen atmosphere, and the information signal was ± 3 V
, Simple matrix drive was performed between 7 and 13V. As a result, a smooth moving image was confirmed by line-sequential driving at a frame frequency of 30 Hz. The luminance half-life when continuously driven under the same conditions was 60 hours.

Embodiment 3 FIG. 3 schematically shows a process of manufacturing an organic EL device having a multicolor light emitting portion of this embodiment. In the figure, 31 is a glass substrate, 32 is an anode, 33a
33c to 33c are charged layers; 34a to 34c are organic compound layers;
5a to 35c are light emitting layers.

In the same manner as in Example 1, I
A TO film is formed by sputtering to a thickness of 70 nm and has a width of 100 μm.
m and a gap of 40 μm are patterned into a stripe of 10 lines to form an anode.

Next, at a position corresponding to the blue pixel portion on the anode 32, an aqueous solution containing 0.1% by weight of the above-described charged material 1 and 5% by weight of methanol was applied at 20 pl / pixel using an ink jet printer. It is applied, washed with water in the same manner as in Example 1, and then dried under vacuum to form a charged layer 33. Thereby, a positively charged layer can be formed at a position corresponding to the blue pixel portion (a-1).

The glass substrate was immersed in the above-described electrolyte solution in which the PPP derivative 2 (n = 10) was anionized for 15 minutes, rinsed with water, dried, and dried.
a is formed (a-2). Thereafter, the PPP derivative 1 (n
= 10) immersed in a cationized electrolyte for 15 minutes,
After rinsing with water and drying, an organic compound layer is formed.
This cycle is repeated 20 times to obtain a P having a thickness of about 100 nm.
A PP derivative layer is formed. About 20 picoliters of a 1% acetic acid aqueous solution is dropped on the outermost cationized PPP dielectric layer by an ink jet method, and oxidation treatment is performed to neutralize it electrically. Therefore, the first light emitting layer 35a can be obtained (a-3). If the neutralization treatment is not performed at this time, there is a problem that a material of another color used in the next step is adsorbed, and thus the oxidation treatment is essential.

In the same manner as in the above steps (a-1) to (a-3), the charge layer 33b is shifted to a position corresponding to a red pixel by shifting the position by 140 μm, and the charge layer 33b having the negative charge property of the negative charge
It is formed using. The surface of the charged layer is negatively charged (b-1).

Next, it is immersed in the electrolyte of the cationic PPP derivative 1 with n = 30, and then immersed in the electrolyte of the anionic PPP derivative 2. Using the first light emitting layer 35a
Light-emitting layer 35b in which the emission color is red-shifted
Can be obtained. Thereafter, as a neutralization treatment, about 20 picoliters of a 1% aqueous solution of ethanolamine (β-aminoethyl alcohol) is dropped on the anionized PPP remaining on the surface by an inkjet method to obtain a second charged layer. (B-3).

Further, similarly, the charging layer 33c is formed using the charging material 1 (c-1), and the light emitting color is more blue than the first light emitting layer 35a using the PPP derivatives 1 and 2 in which n = 5. The shifted third light emitting layer 35c can be obtained. The conditions of the neutralization treatment were the same as before, and a 1% acetic acid solution was dropped by an inkjet method (c-3).

The substrate is transferred into a vacuum chamber having a reduced pressure of 2 × 10 ⁻³ Pa or less, and a mask is arranged as a cathode on the light emitting layers 35 a to 35 c by a resistance heating vapor deposition method so that the substrate is perpendicular to the lower electrode. , Al·Li alloy and Al in a total thickness of about 1
The organic EL element is completed by laminating 10 lines in a stripe shape with 50 nm, width of 100 μm, and gap of 40 μm.

By applying a pulse voltage of +10 volts to the anode side and an AC voltage of ± 3 V to the cathode side of the device and performing matrix driving, light can be emitted from the entire surface. By performing matrix driving between the anode and the cathode, light of each emission color is emitted, and uniform light emission without luminance unevenness is obtained in each light emitting layer and between light emitting layers of the same color.

In this embodiment, the organic compound film is formed by
Although the method of immersion in the electrolytic solution was used, even if an ionic organic compound solution was applied directly on the charged layer by an inkjet method, the wettability was improved by the electric action, and the film thickness distribution was reduced. It is expected that the same effect as the present application can be obtained.

[0092]

As described above, according to the present invention,
An organic compound layer can be selectively formed in a desired region with a uniform thickness, and a plurality of types of organic compound layers can be easily formed on the same substrate. In addition, the thickness of the organic compound layer can be strictly controlled. Therefore, various devices can be configured using the conductive element of the present invention. In particular, by selecting an organic compound material, an organic EL element for full-color display can be provided at a high yield with a simple manufacturing method at a low cost. Becomes

[Brief description of the drawings]

FIG. 1 is a schematic view showing steps of a method for manufacturing a conductive element of the present invention.

FIG. 2 is a diagram illustrating a configuration of an example of an ink jet head used in a method for manufacturing a conductive element of the present invention.

FIG. 3 is a view showing a manufacturing process of the organic EL device according to the example of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Insulating substrate 2, 9 Electrode 3 Charge layer 4, 6 Electrolyte 5, 7, 8 Organic compound layer 10 Base material 14 Groove 15 Heating head 16 Protective layer 17a, 17b Aluminum electrode 18 Heating resistor layer 19 Heat storage layer 20 Substrate DESCRIPTION OF SYMBOLS 21 Ink 22 Orifice 23 Meniscus 24 Ink drop 25 Electrode 31 Glass substrate 32 Anode 33a-33c Charge layer 34a-34c Organic compound layer 35a-35c Light emitting layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Atsushi Kamagaya 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Takao Takiguchi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Co., Ltd. Study F-term (reference) 3-30-2 Shimomaruko, Ota-ku, Tokyo 3K007 AB04 AB17 AB18 BA06 CA01 CB01 DA01 DB03 EB00 FA01 5C094 AA05 AA08 AA42 AA43 AA44 BA12 BA27 CA19 CA24 DA13 EA05 EB02 FA01 FA02 FB01 GB10 5G435 AA04 AA17 BB05 CC09 CC12 HH01 HH20 KK05 KK10

Claims (10)

[Claims] A first electrode formed on a substrate; a charging material disposed on a plurality of regions on the first electrode; an organic compound layer disposed on the charging material; A conductive element comprising a second electrode disposed on a compound layer. 2. The conductive element according to claim 1, further comprising a plurality of different organic compound layers from the charged material on an insulating substrate. 3. The charging material according to claim 1, wherein said charging material comprises an electrolyte.
The conductive element according to claim 1. 4. The conductive element according to claim 3, wherein the electrolyte has a silanol group and an ion-dissociable functional group. 5. The conductive element according to claim 1, wherein the organic compound layer emits light by applying a voltage to the first electrode and the second electrode. 6. A step of applying a charging material on a first electrode disposed on a substrate, and immersing the substrate in an electrolyte containing organic compound ions to adsorb the organic compound ions on the charging material. And forming a second electrode on the organic compound layer. 7. The method according to claim 6, wherein the step of applying the charging material is performed by an ink jet method.
3. The method for producing a conductive element according to claim 1. 8. The method for forming an organic compound layer, wherein the substrate is alternately immersed in an electrolytic solution containing a cation of an organic compound and an electrolytic solution containing an anion of an organic compound to alternately laminate the organic compound layers. The method for manufacturing a conductive element according to claim 6, wherein: 9. The charging material according to claim 6, wherein the charging material comprises an electrolyte.
3. The method for producing a conductive element according to claim 1. 10. The method according to claim 9, wherein the electrolyte has a silanol group and an ion-dissociable functional group.