JPWO2007034900A1 - Organic light emitting device manufacturing method, organic light emitting device, and electronic apparatus - Google Patents

Abstract

An organic light emitting device including at least one carrier transporting layer, and one of the carrier transporting layers is not limited to a solid carrier transporting material but may be formed of a liquid or semi-solid carrier transporting material An object of the present invention is to provide a method for manufacturing a light emitting device, an organic light emitting device having high characteristics manufactured by the method for manufacturing an organic light emitting device, and a highly reliable electronic device. An organic light emitting device (active matrix display device) includes a plurality of organic light emitting elements (organic EL elements) each having a cathode, an electron transport layer, a light emitting layer, a hole transport layer, and an anode. In this organic light emitting device, an anode is formed on an upper substrate, and a cathode, an electron transport layer and a light emitting layer are formed on a TFT circuit substrate by a liquid phase film formation method or a gas phase film formation method, respectively. It joins so that a gap | interval may be formed among them, Then, a hole transport material is inject | poured into a gap | interval, and a hole transport layer is provided and it forms by forming an organic EL element.

Description

  The present invention relates to a method for manufacturing an organic light emitting device, an organic light emitting device, and an electronic apparatus.

  An organic EL (electroluminescence) element (organic light emitting element) has a structure in which an organic layer including a thin film (light emitting layer) containing at least a fluorescent organic compound is sandwiched between a cathode and an anode. It is an element that generates excitons by injecting electrons and holes and recombining them, and emits light by using light emission (fluorescence / phosphorescence) when the excitons are deactivated. .

This organic EL element can emit surface light with a high luminance of about 100 to 100,000 cd / m ² at a low voltage of 10 V or less, and can emit light from blue to red by selecting the type of fluorescent material. It has attracted attention as an element that can realize a large area full color display at low cost.

  The EL phenomenon can also be obtained with a structure in which a single-layer organic thin film is sandwiched between electrodes, but in order to obtain high luminance with a lower voltage applied, the efficiency of carrier (electron and hole) injection from the electrode to the light-emitting layer is improved. It is necessary to let For this reason, a laminated structure in which a carrier transport layer is added between the electrode and the light emitting layer has been proposed for the purpose of reducing the energy barrier between the electrode and the light emitting layer and facilitating carrier movement to the light emitting layer. (For example, see Patent Document 1: Japanese Patent Laid-Open No. 2002-175895).

  By the way, this organic EL element has been conventionally used in various vapor phase film formation methods such as vacuum deposition and chemical vapor deposition (CVD), and various liquid phases such as cast method, spin coating method and ink jet method. It is manufactured by laminating an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode in this order on a single substrate using a film forming method or the like.

  However, when each layer is formed by sequentially laminating, if the previously formed lower layer is not solidified or cured, the upper layer constituent material will mix with the lower layer constituent material, and the upper layer having a uniform interface and The lower layer cannot be formed, and it is difficult to stack the upper layer on the liquid or semi-solid lower layer. Therefore, there is a problem that the selection range of the material used for each layer is narrowed.

  This is a problem particularly in carrier transport layers such as a hole transport layer and an electron transport layer.

  It is an object of the present invention to include at least one carrier transport layer, and one of the carrier transport layers is not limited to a solid carrier transport material, and may be constituted by a liquid or semi-solid carrier transport material. An object of the present invention is to provide a method for manufacturing an organic light-emitting device including an organic light-emitting element, an organic light-emitting device having high characteristics manufactured by the method for manufacturing the organic light-emitting device, and a highly reliable electronic device.

In order to achieve the above object, a method for producing an organic light emitting device of the present invention includes
Of the cathode, anode, light emitting layer and at least one carrier transport layer constituting the organic light emitting device held between the first substrate and the second substrate, other than the carrier transport layer composed of a predetermined carrier transport material A layer is formed by a liquid phase film formation method or a gas phase film formation method, and the carrier transport layer composed of the predetermined carrier transport material is formed by another method, thereby forming the organic light emitting element having a laminated structure. A method of manufacturing an organic light emitting device,
After forming a layer other than the carrier transport layer on the inner surface side of the first substrate and / or the second substrate by a liquid phase film formation method or a gas phase film formation method,
Bonding the first substrate and the second substrate such that a gap is formed between them;
Next, the carrier transport layer is formed by injecting the predetermined carrier transport material into the gap from a first liquid injection section.

  Thus, it is possible to manufacture an organic light-emitting device including an organic light-emitting element that includes at least one carrier transport layer and one of the carrier transport layers can also be configured by a liquid or semi-solid carrier transport material. it can.

  In the method for manufacturing an organic light emitting device of the present invention, it is preferable that the first liquid injection portion is a hole formed in the first substrate or the second substrate.

  As a result, the first liquid injection portion can be formed at a desired position, so that a predetermined carrier transport material can be reliably injected into the target gap position.

  In the method for manufacturing an organic light-emitting device of the present invention, it is preferable that the hole is provided so as not to overlap with a region where the light-emitting layer is formed.

  Thereby, it can prevent reliably that the light emission luminance of an organic light emitting element falls in the area | region in which this hole was provided.

  In the method for manufacturing an organic light emitting device of the present invention, it is preferable that the hole is subjected to a liquid repellent treatment around the hole.

  As a result, it is possible to reliably prevent the predetermined carrier transporting material supplied to the hole from spreading on the substrate on which the hole is formed, and as a result, the predetermined carrier transporting material is inserted into the gap from the hole. Can be injected reliably.

  In the method for manufacturing an organic light-emitting device of the present invention, it is preferable that the hole is formed after a liquid repellent treatment is performed on a region including the region where the hole is formed on the first substrate or the second substrate. .

  Thereby, the liquid repellency can be reliably imparted to the region surrounding the hole in which the first substrate or the second substrate is formed.

  In the method for manufacturing an organic light emitting device of the present invention, it is preferable that a lyophilic treatment is performed on the inside of the hole.

  Thereby, since the lyophilic property inside the hole can be improved, the predetermined carrier transporting material supplied so as to close the hole can be reliably held in the hole.

  In the method for manufacturing an organic light-emitting device according to the present invention, the hole includes a first hole, a second hole that communicates with the first hole on the gap side, and is smaller than a cross section of the first hole. It is preferable that it is comprised.

  Thereby, the predetermined carrier transporting material supplied to the hole can be reliably held in the first hole.

  In the method for manufacturing an organic light emitting device of the present invention, it is preferable that the predetermined carrier transport material is supplied so as to fill the first hole.

  Thus, even if the predetermined carrier transport material is supplied so as to fill the first hole, the hole is formed because the liquid repellent treatment is performed around the hole. It is possible to reliably prevent the carrier transport material from moving to the substrate side.

  In the method for manufacturing an organic light-emitting device of the present invention, a contact angle of the predetermined carrier transport material in the region where the liquid repellent treatment is performed on the first substrate or the second substrate is A [°], and When the contact angle of the predetermined carrier transport material in the first hole is B [°], it is preferable that the relationship of AB ≧ 15 ° is satisfied.

  By satisfying this relationship, even if the predetermined carrier transport material is supplied so as to fill the first hole, the predetermined carrier transport material moves to the substrate side on which the hole is formed. Can be prevented more reliably.

  In the method for manufacturing an organic light-emitting device of the present invention, it is preferable to form a layer other than the carrier transport layer after forming the holes.

  Thereby, it is possible to reliably prevent the influence of heat or the like generated when forming holes in the first substrate or the second substrate from reaching each layer.

  In the method for manufacturing an organic light-emitting device of the present invention, it is preferable that the hole is formed after the layers other than the carrier transport layer are formed and before the first substrate and the second substrate are bonded.

  Thereby, it is possible to reliably prevent or suppress the removal from the first substrate or the second substrate that occurs when the hole is formed remaining in the gap.

  In the method for manufacturing an organic light-emitting device according to the present invention, it is preferable that the hole is formed after the first substrate and the second substrate are bonded.

  As a result, the hole can be formed more accurately in the target region.

  In the method for manufacturing an organic light emitting device according to the present invention, it is preferable that the thickness of the gap is controlled by a spacer.

  Thereby, the first substrate and the second substrate can be bonded in a state where the width of the gap with respect to the thickness direction of the first substrate is substantially constant.

In the method for manufacturing an organic light emitting device of the present invention, the spacer is constituted by a protrusion formed along an outer periphery of a region where the carrier transport layer is formed,
Preferably, the protrusion is provided with a second liquid injection portion for injecting the predetermined carrier transport material injected from the first liquid injection portion into the gap.

  By having the spacer in such a configuration, the function as a spacer can be exhibited, and the function as a barrier layer that prevents the predetermined carrier transporting material from flowing out of the organic light emitting element can be exhibited. Can do.

In the method for manufacturing an organic light emitting device according to the aspect of the invention, the protrusion may contact the first protrusion provided on the first substrate side and the second protrusion provided on the second substrate side. Formed by
The second liquid injecting section lowers the height of a part of the first protrusion and / or the height of a part of the second protrusion, and the first protrusion and the second protrusion It is preferable that it is obtained by contacting.

  Thereby, a protrusion provided with the second liquid injection part can be obtained.

In the method for manufacturing an organic light emitting device according to the aspect of the invention, the protrusion may contact the first protrusion provided on the first substrate side and the second protrusion provided on the second substrate side. Formed by
The second liquid injection part is preferably a through hole provided in one of the first protrusion and the second protrusion.

  Thereby, a protrusion provided with the second liquid injection part can be obtained.

  In the method for manufacturing an organic light emitting device of the present invention, the spacer is preferably composed of particles.

  When the spacer has such a structure, the function as the spacer can be exhibited.

  In the method for manufacturing an organic light-emitting device of the present invention, it is preferable that the particles are disposed in the gap.

  Thereby, the width | variety with respect to the thickness direction of the 1st board | substrate of the space | gap formed can be made substantially constant.

  In the method for manufacturing an organic light emitting device of the present invention, it is preferable to supply the predetermined carrier transporting material to the first liquid injection part by using an ink jet method.

  By using the ink-jet method, it is possible to selectively block each first liquid injection portion with a predetermined carrier transport material, so that waste of the predetermined carrier transport material can be omitted.

  In the method of manufacturing an organic light emitting device according to the present invention, after reducing the atmosphere of the gap and supplying the predetermined carrier transport material so as to close the first liquid injection portion, the pressure between the gap and the atmospheric pressure It is preferable to inject the predetermined carrier transport material into the gap using a pressure difference.

  Thereby, a predetermined carrier transport material can be injected into the gap to form a carrier transport layer composed of this carrier transport material.

In the method for producing an organic light emitting device of the present invention, the pressure difference between the atmospheric pressure and the gap is preferably about 1.0 × 10 ^{−4 to} 1.0 × 10 ¹² Pa.

  Thereby, a predetermined carrier transport material can be reliably injected into the gap.

In the manufacturing method of the organic light emitting device of the present invention, prior to injecting the predetermined carrier transport material supplied so as to close the first liquid injection portion into the gap,
It is preferable to reduce the viscosity of the carrier transport material by heating the predetermined carrier transport material.

  Thereby, even when a solid or semi-solid material having a relatively high viscosity is used as the predetermined carrier transport material, the carrier transport material can be reliably injected into the gap.

  In the method for manufacturing an organic light emitting device of the present invention, it is preferable that the predetermined carrier transport material is heated by heating one or both of the first substrate and the second substrate.

  Thereby, a predetermined carrier transport material can be heated and the viscosity of this carrier transport material can be reliably reduced.

  In the method for manufacturing an organic light emitting device of the present invention, the predetermined carrier transport material is preferably a hole transport material.

  In the method for manufacturing an organic light-emitting device of the present invention, the predetermined carrier transport material includes a hole transport portion having a function of transporting holes and at least one linear alkyl group connected to the hole transport portion. It is preferable that the hole transport material to be used is a main material.

  Since such a compound is a liquid and has a hole transporting material having excellent hole transporting ability, an organic light emitting device obtained by forming a hole transporting layer with such a compound has excellent characteristics. It can be.

The organic light-emitting device manufacturing method of the present invention includes a cathode, an anode, a light-emitting layer, a hole transport layer, and an electron transport layer constituting an organic light-emitting element sandwiched between a first substrate and a second substrate. A layer other than the transport layer is formed by a liquid phase film formation method or a gas phase film formation method, and the hole transport layer composed of a hole transport material is formed by another method, whereby the organic light emitting device having a laminated structure An organic light emitting device manufacturing method for manufacturing
Forming the anode on the first substrate;
Forming a first protrusion on the anode along the outer periphery of the region where the hole transport layer is to be formed and so that a part of the height thereof is lowered;
Forming a second protrusion on the second substrate along an outer periphery of a region where the hole transport layer is formed;
Forming the cathode, the electron transport layer, and the light emitting layer in this order on the second substrate exposed inside the second protrusion;
A gap between the first substrate and the second substrate, and a second liquid injection part for injecting the hole transport material into the gap between the first protrusion and the second protrusion Contacting the first protrusion and the second protrusion so that each is formed,
Bonding the first substrate and the second substrate by forming a sealing portion that seals the gap at their edges; and
Forming a first liquid injection portion by providing a hole in the thickness direction in the first substrate so as not to overlap a region where the light emitting layer is formed;
Depressurizing the gap;
Supplying the hole transport material so as to block the first liquid injection part;
Utilizing the difference in pressure between the gap and atmospheric pressure to form the hole transport layer by injecting the hole transport material into the gap;
Sealing the first liquid injection part.

  Accordingly, an organic light emitting device including a hole transport layer and an organic light emitting device that can be configured not only by a solid hole transport material but also by a liquid or semi-solid hole transport material. Can be manufactured.

The method for producing an organic light emitting device of the present invention includes electron transport among a cathode, an anode, a light emitting layer, a hole transport layer, and an electron transport layer constituting an organic light emitting element sandwiched between a first substrate and a second substrate. A layer other than the layers is formed by a liquid phase film formation method or a gas phase film formation method, and the electron transport layer composed of an electron transport material is formed by another method, thereby manufacturing the organic light-emitting element having a stacked structure. A method of manufacturing an organic light emitting device,
Forming the anode on the first substrate;
Forming a first protrusion on the anode along the outer peripheral portion of the region where the electron transport layer is formed and so that a part of the height thereof is lowered;
Forming a second protrusion on the second substrate along an outer periphery of a region where the electron transport layer is formed;
On the anode exposed inside the first protrusion, the hole transport layer and the light emitting layer are formed in this order, and on the second substrate exposed inside the second protrusion, Forming the cathode;
There is a gap between the first substrate and the second substrate, and a second liquid injection section for injecting the electron transport material into the gap between the first protrusion and the second protrusion. Bringing the first protrusion and the second protrusion into contact with each other so as to be formed respectively;
Bonding the first substrate and the second substrate by forming a sealing portion that seals the gap at their edges; and
Forming a first liquid injection portion by providing a hole in the thickness direction in the first substrate so as not to overlap a region where the light emitting layer is formed;
Depressurizing the gap;
Supplying the electron transport material so as to block the first liquid injection part;
Using the difference in pressure between the gap and atmospheric pressure to form the electron transport layer by injecting the electron transport material into the gap;
Sealing the first liquid injection part.

  Thus, it is possible to manufacture an organic light-emitting device that includes an electron transport layer and includes an organic light-emitting element that can be configured not only by a solid electron transport material but also by a liquid or semi-solid electron transport material. it can.

The organic light-emitting device manufacturing method of the present invention includes a cathode, an anode, a light-emitting layer, a hole transport layer, and an electron transport layer constituting an organic light-emitting element sandwiched between a first substrate and a second substrate. A layer other than the transport layer is formed by a liquid phase film formation method or a gas phase film formation method, and the hole transport layer composed of a hole transport material is formed by another method, whereby the organic light emitting device having a laminated structure An organic light emitting device manufacturing method for manufacturing
Forming the anode on the first substrate;
Forming a first protrusion on the anode along the outer periphery of the region where the hole transport layer is to be formed and so that a part of the height thereof is lowered;
Applying a liquid repellent treatment to the surface of the first substrate opposite to the anode;
A step of forming a first liquid injection part by providing a hole in the thickness direction in the first substrate that has been subjected to the liquid repellent treatment so as not to overlap with a region where the light emitting layer is to be formed. When,
Forming a second protrusion on the second substrate along an outer periphery of a region where the hole transport layer is formed;
Forming the cathode, the electron transport layer, and the light emitting layer in this order on the second substrate exposed inside the second protrusion;
A gap between the first substrate and the second substrate, and a second liquid injection part for injecting the hole transport material into the gap between the first protrusion and the second protrusion Contacting the first protrusion and the second protrusion so that each is formed,
Bonding the first substrate and the second substrate by forming a sealing portion that seals the gap at their edges; and
Depressurizing the gap;
Supplying the hole transport material so as to block the first liquid injection part;
Utilizing the difference in pressure between the gap and atmospheric pressure to form the hole transport layer by injecting the hole transport material into the gap;
Sealing the first liquid injection part.

  Accordingly, an organic light emitting device including a hole transport layer and an organic light emitting device that can be configured not only by a solid hole transport material but also by a liquid or semi-solid hole transport material. Can be manufactured.

The method for producing an organic light emitting device of the present invention includes electron transport among a cathode, an anode, a light emitting layer, a hole transport layer, and an electron transport layer constituting an organic light emitting element sandwiched between a first substrate and a second substrate. A layer other than the layers is formed by a liquid phase film formation method or a gas phase film formation method, and the electron transport layer composed of an electron transport material is formed by another method, thereby manufacturing the organic light-emitting element having a stacked structure. A method of manufacturing an organic light emitting device,
Forming the anode on the first substrate;
Forming a first protrusion on the anode along the outer peripheral portion of the region where the electron transport layer is formed and so that a part of the height thereof is lowered;
Applying a liquid repellent treatment to the surface of the first substrate opposite to the anode;
A step of forming a first liquid injection part by providing a hole in the thickness direction in the first substrate that has been subjected to the liquid repellent treatment so as not to overlap with a region where the light emitting layer is to be formed. When,
Forming a second protrusion on the second substrate along an outer periphery of a region where the electron transport layer is formed;
On the anode exposed inside the first protrusion, the hole transport layer and the light emitting layer are formed in this order, and on the second substrate exposed inside the second protrusion, Forming the cathode;
There is a gap between the first substrate and the second substrate, and a second liquid injection section for injecting the electron transport material into the gap between the first protrusion and the second protrusion. Bringing the first protrusion and the second protrusion into contact with each other so as to be formed respectively;
Bonding the first substrate and the second substrate by forming a sealing portion that seals the gap at their edges; and
Depressurizing the gap;
Supplying the electron transport material so as to block the first liquid injection part;
Using the difference in pressure between the gap and atmospheric pressure to form the electron transport layer by injecting the electron transport material into the gap;
Sealing the first liquid injection part.

  Thus, it is possible to manufacture an organic light-emitting device that includes an electron transport layer and includes an organic light-emitting element that can be configured not only by a solid electron transport material but also by a liquid or semi-solid electron transport material. it can.

  In the manufacturing method of the organic light-emitting device of this invention, it is preferable to provide two or more said organic light emitting elements.

  Also in manufacturing an organic light emitting device having such a configuration, a carrier transport layer can be formed corresponding to each organic light emitting element.

  In the method for manufacturing an organic light-emitting device of the present invention, it is preferable that a carrier transport layer constituting the organic light-emitting element is formed integrally with the plurality of organic light-emitting elements.

  The organic light emitting device of the present invention is manufactured by the method for manufacturing an organic light emitting device of the present invention.

  Thereby, a light emitting device having excellent characteristics can be obtained.

  An electronic apparatus according to the present invention includes the organic light-emitting device according to the present invention.

  As a result, a highly reliable electronic device can be obtained.

FIG. 1 is a longitudinal sectional view showing a first embodiment of an active matrix display device to which the light emitting device of the present invention is applied. FIG. 2 is a perspective view showing a first embodiment of an active matrix display device to which the light emitting device of the present invention is applied. FIG. 3 is a diagram for explaining a method of manufacturing the active matrix display device shown in FIG. FIG. 4 is a diagram for explaining a method of manufacturing the active matrix display device shown in FIG. FIG. 5 is a diagram for explaining a method of manufacturing the active matrix display device shown in FIG. FIG. 6 is a longitudinal sectional view showing a second embodiment of an active matrix display device to which the organic light emitting device of the present invention is applied. FIG. 7 is a perspective view showing a second embodiment of an active matrix display device to which the organic light emitting device of the present invention is applied. FIG. 8 is a plan view showing a second embodiment of an active matrix display device to which the organic light emitting device of the present invention is applied. FIG. 9 is a diagram for explaining a method of manufacturing the active matrix display device shown in FIG. FIG. 10 is a diagram for explaining a method of manufacturing the active matrix display device shown in FIG. FIG. 11 is a diagram for explaining a method of manufacturing the active matrix display device shown in FIG. FIG. 12 is a longitudinal sectional view showing a third embodiment of an active matrix display device to which the light emitting device of the present invention is applied. FIG. 13 is a longitudinal sectional view showing a fourth embodiment of an active matrix display device to which the light emitting device of the present invention is applied. FIG. 14 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which the electronic apparatus of the present invention is applied. FIG. 15 is a perspective view showing a configuration of a mobile phone (including PHS) to which the electronic apparatus of the invention is applied. FIG. 16 is a perspective view showing a configuration of a digital still camera to which the electronic apparatus of the present invention is applied.

  Hereinafter, a method for manufacturing an organic light emitting device, an organic light emitting device, and an electronic apparatus according to the present invention will be described in detail with reference to the accompanying drawings.

<First Embodiment>
First, a first embodiment of an active matrix display device to which the organic light emitting device of the present invention is applied will be described. In the present embodiment, when the hole transport layer 6 is provided so as to correspond to the shape of each organic EL element 1, that is, the hole transport layer 6 is provided individually for each organic EL element 1. A description will be given of a case where the

  1 and 2 are views showing a first embodiment of an active matrix display device to which an organic light-emitting device of the present invention is applied. FIG. 1 is a longitudinal sectional view, and FIG. 2 is a perspective view. 3 to 5 are views for explaining a method of manufacturing the active matrix display device shown in FIGS. 2 is shown upside down with respect to the display device of FIG. 1 for convenience of explanation, and the description of the substrate 20 and the sealing portion 74 is omitted. In the following description, the upper side in FIGS. 1 to 5 is referred to as “upper” and the lower side is referred to as “lower”.

  An active matrix type display device (hereinafter simply referred to as “display device”) 10 shown in FIGS. 1 and 2 includes a TFT circuit substrate (counter substrate) 20 and an organic light emitting element 1 provided on the substrate 20. And an upper substrate 9 (first substrate) facing the TFT circuit substrate 20 (second substrate).

  The TFT circuit substrate 20 includes a substrate 21 and a circuit unit 22 formed on the substrate 21.

  The substrate 21 serves as a support for each part constituting the display device 10, and the upper substrate 9 functions as, for example, a protective layer for protecting the organic light emitting element 1.

  In addition, since the display device 10 according to the present embodiment has a configuration for extracting light from the substrate 21 side (bottom emission type), the substrate 21 is substantially transparent (colorless transparent, colored transparent, translucent). The upper substrate 9 is not particularly required to be transparent.

  Various glass material substrates are suitable for the substrate 21, but various high-hardness resin substrates can also be used.

  On the other hand, the upper substrate 9 is made of, for example, a polyether resin such as a polyimide resin, a polyester resin, a polyamide resin, a polyether ether ketone, or a polyether sulfone other than those listed as the constituent materials of the substrate 21. A substrate configured as a main material can be used. Especially, since the polyimide resin has a small coefficient of thermal expansion and thermal contraction, a substrate mainly made of polyimide resin can keep the thermal contraction rate low. Moreover, the board | substrate comprised using a polyester-type resin as a main material has the advantage that dimensional stability is good.

  Furthermore, the shrinkage rate of the upper substrate 9 can be reduced and the dimensional stability can be improved by laminating fillers and fibers in such a resin material, or by adjusting the pre-heat treatment and the degree of crosslinking. .

  As the constituent material of the upper substrate 9, in addition to the materials described above, for example, a carbon-based material such as a ceramic material, a metal material, carbon fiber, or the like can be used.

  Although the average thickness of the board | substrate 21 is not specifically limited, It is preferable that it is about 0.1-30 mm, and it is more preferable that it is about 0.5-2.0 mm. On the other hand, the average thickness of the upper substrate 9 is not particularly limited, but is preferably about 0.1 to 30 mm, and more preferably about 0.1 to 10 mm.

  The circuit unit 22 includes a base protective layer 23 formed on the substrate 21, a driving TFT (switching element) 24 formed on the base protective layer 23, a first interlayer insulating layer 25, and a second interlayer insulating layer. 26.

  The driving TFT 24 includes a semiconductor layer 241, a gate insulating layer 242 formed on the semiconductor layer 241, a gate electrode 243 formed on the gate insulating layer 242, a source electrode 244, and a drain electrode 245. ing.

  The organic light emitting element 1 is provided on the circuit portion 22 corresponding to each driving TFT 24. Adjacent organic light emitting elements 1 are partitioned by protrusions (banks) 7.

  In the present embodiment, the cathode 3 of each organic light emitting element 1 constitutes a pixel electrode and is electrically connected to the drain electrode 245 of each driving TFT 24 by the wiring 27. In addition, the organic semiconductor layer composed of the electron transport layer 4, the light emitting layer 5, and the hole transport layer 6 is formed individually for each organic light emitting element 1, and the hole transport layer 6 is in a liquid, semi-solid state. It can also be constituted by a solid or solid hole transport material. Further, the anode 8 is a common electrode.

  The display device 10 may be a single color display. For example, the light emitting material used for the light emitting layer 5 for each organic light emitting element 1 may be red. Color display is also possible by appropriately selecting any one of the light emitting material, the green light emitting material, and the blue light emitting material.

  Hereinafter, the organic light emitting device 1 will be described in detail.

  As shown in FIG. 1, the organic light emitting device 1 includes an electron transport layer 4, a light emitting layer 5, and a hole transport layer in order from the cathode 3 side between the cathode 3, the anode 8, and the cathode 3 and the anode 8. 6 is inserted.

  The cathode 3 is an electrode that injects electrons into the electron transport layer 4.

  As a constituent material (cathode material) of the cathode 3, a material having a small work function is preferably used.

  Examples of such cathode materials include Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, Yb, Ag, Cu, Al, Cs, Rb, and alloys containing these, and the like. At least one of them can be used.

  In particular, when an alloy is used as the cathode material, an alloy containing a stable metal element such as Ag, Al, or Cu, specifically, an alloy such as MgAg, AlLi, or CuLi is preferably used. By using such an alloy as a cathode material, the electron injection efficiency and stability of the cathode 3 can be improved.

  The average thickness of the cathode 3 is not particularly limited, but is preferably about 100 nm to 3000 nm, and more preferably about 500 to 2000 nm. If the thickness of the cathode 3 is too thin, the function of the cathode 3 may not be sufficiently exhibited. On the other hand, if the cathode 3 is too thick, the light transmittance may be significantly reduced depending on the type of the cathode material, When the configuration of the organic EL element 1 is a bottom emission type, it may not be suitable for practical use.

  On the other hand, the anode 8 is an electrode that injects holes into the hole transport layer 6.

  As a constituent material (anode material) of the anode 8, it is preferable to use a material having a large work function and excellent conductivity.

Examples of such an anode material include ITO (composite of indium oxide and zinc oxide), oxides such as SnO ₂ , Sb-containing SnO ₂ , and Al-containing ZnO, Au, Pt, Ag, Cu, or these. An alloy etc. are mentioned, At least 1 sort (s) of these can be used.

  The average thickness of the anode 8 is not particularly limited, but is preferably about 10 to 200 nm, and more preferably about 50 to 150 nm. If the thickness of the anode 8 is too thin, the function as the anode 8 may not be sufficiently exhibited. On the other hand, if the anode 8 is too thick, the light emission efficiency of the organic EL element 1 may be reduced.

  As the anode material, for example, a conductive resin material such as polythiophene or polypyrrole can be used.

  Between the cathode 3 and the anode 8, an electron transport layer 4, a light emitting layer 5, and a hole transport layer 6 are provided as organic semiconductor layers, and these are formed on the cathode 3 in this order.

  The electron transport layer 4 is a layer having a function of transporting electrons injected from the cathode 3 to the light emitting layer 5.

As a constituent material (electron transport material) of the electron transport layer 4, for example, 1,3,5-tris [(3-phenyl-6-tri-fluoromethyl) quinoxalin-2-yl] benzene (TPQ1), 1, Benzene compounds (starburst compounds) such as 3,5-tris [{3- (4-t-butylphenyl) -6-trisfluoromethyl} quinoxalin-2-yl] benzene (TPQ2), such as naphthalene Naphthalene compounds, phenanthrene compounds such as phenanthrene, chrysene compounds such as chrysene, perylene compounds such as perylene, anthracene compounds such as anthracene, pyrene compounds such as pyrene, acridines such as acridine Compounds, stilbene compounds such as stilbene, thiophenes such as BBOT Compounds, butadiene compounds such as butadiene, coumarin compounds such as coumarin, quinoline compounds such as quinoline, bistyryl compounds such as bistyryl, pyrazine compounds such as pyrazine and distyrylpyrazine, quinoxalines and the like Quinoxaline compounds, benzoquinone, benzoquinone compounds such as 2,5-diphenyl-para-benzoquinone, naphthoquinone compounds such as naphthoquinone, anthraquinone compounds such as anthraquinone, oxadiazole, 2- (4-biphenylyl)- Oxadiazole compounds such as 5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD), TPOB, BMD, BND, BDD, BAPD, triazole, 3,4,5- Triphenyl-1,2,4-to Triazole compounds such as azole, oxazole compounds, anthrone compounds such as anthrone, fluorenone, fluorenone compounds such as 1,3,8-trinitro-fluorenone (TNF), diphenoquinone, diphenoquinone compounds such as MBDQ , Stilbene quinone, stilbene quinone compounds such as MBSQ, anthraquinodimethane compounds, thiopyran dioxide compounds, fluorenylidene methane compounds, diphenyldicyanoethylene compounds, fluorene compounds such as fluorene, phthalocyanines, Metal or metal-free phthalocyanine compounds such as copper phthalocyanine and iron phthalocyanine, 8-hydroxyquinoline aluminum (Alq ₃ ), benzoxazole and benzothiazole as ligands And various metal complexes such as the complex.

  In addition, as a constituent material (electron transport material) of the electron transport layer 4, for example, a polymer material such as an oxadiazole polymer (polyoxadiazole) or a triazole polymer (polytriazole) is used. You can also.

  Although the average thickness of the electron carrying layer 4 is not specifically limited, It is preferable that it is about 1-100 nm, and it is more preferable that it is about 20-50 nm.

  In addition, you may make it provide the electron injection layer which improves the electron injection efficiency from the cathode 3, for example between the electron carrying layer 4 and the cathode 3. FIG.

  Examples of the constituent material (electron injection material) of the electron injection layer include 8-hydroxyquinoline, oxadiazole, or derivatives thereof (for example, metal chelate oxinoid compounds containing 8-hydroxyquinoline). These can be used alone or in combination of two or more thereof (for example, as a multi-layer laminate, etc.), and various inorganic insulating materials, various inorganic semiconductor materials, and the like can be used.

  By configuring the electron injection layer using an inorganic insulating material or an inorganic semiconductor material as a main material, current leakage can be effectively prevented, electron injection performance can be improved, and durability can be improved.

  Examples of such inorganic insulating materials include alkali metal chalcogenides (oxides, sulfides, selenides, tellurides), alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides. Of these, one or two or more of these can be used in combination. By forming the electron injection layer using these as main materials, the electron injection property can be further improved.

Examples of the alkali metal chalcogenide include Li ₂ O, LiO, Na ₂ S, Na ₂ Se, and NaO.

  Examples of the alkaline earth metal chalcogenide include CaO, BaO, SrO, BeO, BaS, MgO, and CaSe.

  Examples of the alkali metal halide include CsF, LiF, NaF, KF, LiCl, KCl, and NaCl.

Examples of the alkaline earth metal halide include CaF ₂ , BaF ₂ , SrF ₂ , MgF ₂ , and BeF ₂ .

  Examples of the inorganic semiconductor material include an oxide containing at least one element of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn. , Nitrides, oxynitrides, and the like, and one or more of these can be used in combination.

  Moreover, when an electron injection layer is comprised with such an inorganic material, it is preferable that this inorganic material is a microcrystal or an amorphous | non-crystalline substance. Thereby, since the electron injection layer becomes more uniform, pixel defects such as dark spots can be reduced.

  The hole transport layer 6 has a function of transporting holes injected from the anode 8 to the light emitting layer 5.

  In the present embodiment, the hole transport layer is not limited to a solid hole transport material by applying the method of manufacturing an organic light emitting device of the present invention described below to manufacture the display device 10. It can also be constituted by a liquid or semi-solid hole transport material.

Among the hole transport materials constituting the hole transport layer 6, examples of solid materials at room temperature include 1,1-bis (4-di-para-triaminophenyl) cyclohexane, 1,1 ′. Arylcycloalkane compounds such as bis (4-di-para-tolylaminophenyl) -4-phenyl-cyclohexane, 4,4 ′, 4 ″ -trimethyltriphenylamine, N, N, N ′, N '-Tetraphenyl-1,1'-biphenyl-4,4'-diamine, N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4' -Diamine (TPD1), N, N'-diphenyl-N, N'-bis (4-methoxyphenyl) -1,1'-biphenyl-4,4'-diamine (TPD2), N, N, N ', N′-tetrakis (4-methoxyphenyl) -1,1′-biphe Nyl-4,4′-diamine (TPD3), N, N′-di (1-naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine (α-NPD), TPTE, arylamine compounds such as 4,4 ′, 4 ″ -tris (1-naphthylphenylamino) triphenylamine (1-TNATA), N, N, N ′, N′-tetraphenyl-para- Of phenylenediamine, N, N, N ′, N′-tetra (para-tolyl) -para-phenylenediamine, N, N, N ′, N′-tetra (meta-tolyl) -meta-phenylenediamine (PDA) Phenylenediamine compounds such as carbazole, N-isopropylcarbazole, carbazole compounds such as N-phenylcarbazole, stilbene, and stilbs such as 4-di-para-tolylaminostilbene Emissions-based compounds, oxazole-based compounds such as O x _Z, triphenylmethane, triphenylmethane compounds such as m-MTDATA, 1-phenyl-3- (para - dimethylaminophenyl) pyrazoline compounds such as pyrazoline Benzine (cyclohexadiene) compounds, triazole compounds such as triazole, imidazole compounds such as imidazole, 1,3,4-oxadiazole, 2,5-di (4-dimethylaminophenyl) -1, Oxadiazole compounds such as 3,4, -oxadiazole, anthracene, anthracene compounds such as 9- (4-diethylaminostyryl) anthracene, fluorenone, 2,4,7, -trinitro-9-fluorenone, 2,7-bis (2-hydroxy-3- (2-chloroph Nylcarbamoyl) -1-naphthylazo) fluorenone compounds such as fluorenone, aniline compounds such as polyaniline, silane compounds, 1,4-dithioketo-3,6-diphenyl-pyrrolo- (3,4-c) pyrrolo A pyrrole compound such as pyrrole, a fluorene compound such as fluorene, a porphyrin, a porphyrin compound such as metal tetraphenylporphyrin, a quinacridone compound such as quinacridone, phthalocyanine, copper phthalocyanine, tetra (t-butyl) copper phthalocyanine Metal or metal-free phthalocyanine compounds such as iron phthalocyanine, copper naphthalocyanine, vanadyl naphthalocyanine, metal or metal-free naphthalocyanine compounds such as monochlorogallium naphthalocyanine, N, '- di (naphthalene-1-yl) -N, N'- diphenyl - benzidine, N, N, N', compounds of low molecular weight of the benzidine type compound such as N'- tetraphenyl benzidine and the like.

  In addition, the hole transport material that is liquid or semi-solid at room temperature is not particularly limited, but includes a hole transport material (low molecular weight compound) that is solid at room temperature as described above as a hole transport part, And what has at least 1 linear alkyl group connected with this hole transport part is used suitably. By introducing a linear alkyl group into the hole transport part, that is, a solid hole transport material, the melting point and glass transition temperature of the resulting compound are lowered without reducing the hole transport ability of the hole transport part. be able to. In addition, since the melting point and the glass transition temperature can be controlled by a relatively easy method of adjusting the chain length (molecular weight) of the linear alkyl group and the number to be introduced, the production of the organic light-emitting device of the present invention described later is performed. In the method, it can be suitably used as a hole transport material that is liquid or semi-solid at room temperature.

  Specifically, examples of the hole transport material that is liquid or semi-solid at room temperature include, for example, a compound represented by the following general formula (A1) (hereinafter, this compound is referred to as “compound (A1)”). It is done.

[Wherein, X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom or a linear alkyl group, and may be the same or different. However, at least one of X ¹ , X ² , X ³ and X ⁴ represents a linear alkyl group having 3 to 8 carbon atoms, and the other represents a hydrogen atom, a methyl group or an ethyl group. The eight R's each independently represent a hydrogen atom, a methyl group or an ethyl group, and may be the same or different, and Y represents at least a substituted or unsubstituted aromatic hydrocarbon ring. Represents a group containing one. ]
Such a compound (A1) has an excellent hole transport ability and is in a liquid or semi-solid form at room temperature.

In the compound (A1), the substituent X ¹ , the substituent X ² , the substituent X ³ and the substituent X ⁴ (hereinafter, these may be collectively referred to as “substituent X”). At least one, preferably 2, more preferably 3, and even more preferably 4 are straight-chain alkyl groups having 3 to 8 carbon atoms.

  By introducing a linear alkyl group having 3 to 8 carbon atoms and increasing the number thereof, the melting point and glass transition temperature of the compound (A1) are lowered. In addition, since an interaction occurs between the substituents X, crystallization of this compound is suppressed, and an amorphous state is easily obtained. Thereby, the viscosity of a compound (A1) can be reduced reliably.

  In addition, since the main skeleton of the compound (A1) has a conjugated chemical structure, carriers are smoothly transferred between the compounds due to the spread of its unique electron cloud. Thereby, a compound (A1) exhibits the outstanding carrier transport ability.

  Moreover, as for the carbon number of the said linear alkyl group, it is more preferable that it is 3-6. When the carbon number of the linear alkyl group becomes too small, the interaction between the substituents X becomes small, which may result in a compound (A1) that is difficult to become amorphous. As a result, the compound (A1) may be in a solid state.

  On the other hand, when the carbon number of the linear alkyl group becomes too large, the main skeletons of the compound (A1) are difficult to approach each other, and there is a possibility that carriers are not sufficiently transferred between the main skeletons.

Furthermore, when two of the substituents X are linear alkyl groups having 3 to 8 carbon atoms, the substituents X ¹ and X ³ are linear alkyl groups having 3 to 8 carbon atoms. Is preferred. Thereby, since the interaction between the substituents X occurs more reliably, the viscosity of the compound (A1) can be reliably reduced.

  Moreover, when several of the substituents X are C3-C8 linear alkyl groups, it is preferable that each substituent X is the thing of substantially the same carbon number, and the thing of the same carbon number It is more preferable that Thereby, it can prevent or suppress that dispersion | variation arises in the separation distance of compounds (A1), ie, main skeletons. As a result, it is possible to suitably prevent bias in the delivery of holes in each part of the hole transport material. In other words, the hole transport ability in each part of the hole transport layer 6 becomes more uniform.

  The substituent X may be bonded to any position from the 2-position to the 6-position of the benzene ring, but is particularly preferably bonded to any one of the 3-position, 4-position or 5-position. . Thereby, while interaction of substituent X comes to occur more reliably, compound (A1) can be spaced apart at a more suitable distance. Thereby, it can prevent reliably that hole transport reduces, reducing the viscosity of hole transport material.

  In addition, among the substituent X, those other than those having a linear alkyl group having 3 to 8 carbon atoms represent a hydrogen atom, a methyl group or an ethyl group, and these selections are straight chain alkyl having 3 to 8 carbon atoms. What is necessary is just to make it according to carbon number of the substituent X showing group. For example, when the number of carbon atoms of the substituent X representing a straight-chain alkyl group having 3 to 8 carbon atoms is large, other than that, a hydrogen atom is selected and a straight-chain alkyl group having 3 to 8 carbon atoms is represented. When the substituent X has a small number of carbon atoms, other than that, a methyl group or an ethyl group may be selected.

  Next, the main skeleton that contributes to hole transport in the compound (A1) will be described.

  The substituent R is a hydrogen atom, a methyl group or an ethyl group, and the substituent R may be selected according to the number of carbon atoms of the substituent X. For example, when the carbon number of the substituent X is large, a hydrogen atom is selected as the substituent R, and when the carbon number of the substituent X is small, the substituent R is a methyl group or an ethyl group. You may make it choose.

  The group Y may be any group as long as it contains at least one substituted or unsubstituted aromatic hydrocarbon ring, and is particularly preferably composed of a carbon atom and a hydrogen atom. Thereby, since the delivery of holes between the compounds (A1) is surely performed, the compound (A1) exhibits an excellent hole transporting ability.

  Specifically, examples of the structure including at least one aromatic hydrocarbon ring include those represented by the following chemical formulas (B1) to (B17).

  Further, the total number of carbon atoms of the group Y is preferably 6-30, more preferably 10-25, and even more preferably 10-20.

  Further, in the group Y, the number of aromatic hydrocarbon rings is preferably 1 to 5, more preferably 2 to 5, and even more preferably 2 or 3.

  In view of these, in the compound (A1), as the group Y, a biphenylene group or a derivative thereof is a particularly preferable structure.

  Thereby, since the hole delivery between the compounds (A1) is more reliably performed, the hole transport material has a more excellent hole transport ability.

  In addition, in the group Y, when a substituent is introduced into the aromatic hydrocarbon ring, the substituent is not particularly limited as long as the planarity of the group Y can be maintained. A linear alkyl group is preferable, and a methyl group or an ethyl group is more preferable.

  In the present invention, the hole transport material is a liquid or semi-solid at a normal temperature when it is a low molecule (monomer or oligomer), but the low molecule is polymerized by polymerizing the low molecules. A solid material can also be used. When such a hole transport material is used, in the method for manufacturing the light emitting device 10 described later, when the hole transport layer 6 is formed, the hole transport material is in a liquid or semi-solid (low molecule) state. The solid hole transport layer 6 can be formed in the gap 76 by injecting into the gap 76 from one liquid injection portion 77 and polymerizing (curing) this hole transport material. Thus, the hole transport material can be polymerized to improve the heat resistance of the hole transport material. Furthermore, diffusion of the hole transport material (low molecule) into the light emitting layer 5 can be suitably prevented.

  Such a hole transport material is not particularly limited, but, for example, a material having a polymerizable group at the terminal of a linear alkyl group that the liquid or semisolid hole transport material at room temperature as described above has is suitable. Used for.

  The polymerizable group is not particularly limited as long as it undergoes a predetermined treatment so that the polymerizable groups can undergo a polymerization reaction and the adjacent hole transport materials can be linked to each other. For example, an epoxy group, an oxetane group, ( Examples thereof include a (meth) acryloyl group, a vinyl ether group, and a vinyl benzyl ether group, and one or more of these can be used in combination.

  Specific examples include those in which the substituent X included in the compound (A1) is shown below.

That is, the substituent X ¹ , the substituent X ² , the substituent X ³ and the substituent X ⁴ are each independently a hydrogen atom, a methyl group, an ethyl group or the following general formula (B1) to the following general formula (B4). Any one of the substituents represented by the formula: However, at least one of the substituent X ¹ , the substituent X ² , the substituent X ³ and the substituent X ⁴ is a substituent represented by the following general formula (B1) to the following general formula (B4). Represents one of the following.

[In these formulas, n ¹ represents an integer of 2 to 8. n ² represents an integer of 3 to 8, m represents an integer of 0 to 3. Z ¹ represents a hydrogen atom or a methyl group, and Z ² represents a hydrogen atom, a methyl group or an ethyl group. ]

  The average thickness of the hole transport layer 6 is not particularly limited, but is preferably about 10 to 150 nm, and more preferably about 50 to 100 nm.

  Note that a hole injection layer that improves the hole injection efficiency from the anode 8 may be provided between the anode 8 and the hole transport layer 6, for example.

  As a constituent material (hole injection material) of this hole injection layer, for example, copper phthalocyanine, 4,4 ′, 4 ″ -tris (N, N-phenyl-3-methylphenylamino) triphenylamine ( m-MTDATA) and the like.

  Here, when an electric current (voltage is applied) is applied between the anode 8 and the cathode 3, holes move in the hole transport layer 6 and electrons move in the electron transport layer 4, and holes in the light emitting layer 5 are transferred. And electrons recombine. And in the light emitting layer 5, an exciton (exciton) produces | generates, and when this exciton returns to a ground state, energy (fluorescence and phosphorescence) is discharge | released (light emission).

  As a constituent material (light emitting material) of the light emitting layer 5, various polymer materials and various low molecular materials can be used alone or in combination.

  Examples of the polymer light-emitting material include polyacetylene compounds such as trans-type polyacetylene, cis-type polyacetylene, poly (di-phenylacetylene) (PDPA), poly (alkyl, phenylacetylene) (PAPA), and poly (para-para-). Fenvinylene) (PPV), poly (2,5-dialkoxy-para-phenylenevinylene) (RO-PPV), cyano-substituted-poly (para-phenvinylene) (CN-PPV), poly (2-dimethyloctyl) Polyparaphenylene vinylene compounds such as silyl-para-phenylene vinylene (DMOS-PPV), poly (2-methoxy, 5- (2′-ethylhexoxy) -para-phenylene vinylene) (MEH-PPV), poly ( 3-alkylthiophene) (PAT), poly (oxypropylene) Polythiophene compounds such as riol (POPT), poly (9,9-dialkylfluorene) (PDAF), α, ω-bis [N, N′-di (methylphenyl) aminophenyl] -poly [9,9- Bis (2-ethylhexyl) fluorene-2,7-diyl] (PF2 / 6am4), poly (9,9-dioctyl-2,7-divinylenefluorenyl-ortho-co (anthracene-9,10-diyl) Polyfluorene compounds such as poly (para-phenylene) (PPP), polyparaphenylene compounds such as poly (1,5-dialkoxy-para-phenylene) (RO-PPP), poly (N-vinyl) Polycarbazole compounds such as carbazole (PVK), poly (methylphenylsilane) (PMPS), poly (naphthylphenylsilane) PnPs), polysilane-based compounds such as poly (biphenylyl phenyl silane) (pBPS), and the like.

On the other hand, examples of low-molecular light-emitting materials include benzene-based compounds such as distyrylbenzene (DSB) and diaminodistyrylbenzene (DADSB), naphthalene-based compounds such as naphthalene and nile red, and phenanthrene-based materials such as phenanthrene. Compound, chrysene, chrysene compounds such as 6-nitrochrysene, perylene, N, N'-bis (2,5-di-t-butylphenyl) -3,4,9,10-perylene-di-carboximide Perylene compounds such as (BPPC), coronene compounds such as coronene, anthracene compounds such as anthracene and bisstyrylanthracene, pyrene compounds such as pyrene, 4- (di-cyanomethylene) -2-methyl Of 6- (para-dimethylaminostyryl) -4H-pyran (DCM) Such as pyran compounds, acridine compounds such as acridine, stilbene compounds such as stilbene, thiophene compounds such as 2,5-dibenzoxazole thiophene, benzoxazole compounds such as benzoxazole, and benzimidazole Benzoimidazole compounds, benzothiazole compounds such as 2,2 ′-(para-phenylenedivinylene) -bisbenzothiazole, bistyryl (1,4-diphenyl-1,3-butadiene), tetraphenylbutadiene, etc. Butadiene compounds, naphthalimide compounds such as naphthalimide, coumarin compounds such as coumarin, perinone compounds such as perinone, oxadiazole compounds such as oxadiazole, aldazine compounds, 1, 2 , 3 , 4,5-pentaphenyl-1,3-cyclopentadiene (PPCP), a cyclopentadiene compound such as quinacridone and quinacridone red, a pyridine compound such as pyrrolopyridine and thiadiazolopyridine, Spiro compounds such as 2,2 ′, 7,7′-tetraphenyl-9,9′-spirobifluorene, metal or metal-free phthalocyanine compounds such as phthalocyanine (H ₂ Pc), copper phthalocyanine, fluorene Such a fluorene-based compound, 8-hydroxyquinoline aluminum (Alq ₃ ), tris (4-methyl-8 quinolinolate) aluminum (III) (Almq ₃ ), 8-hydroxyquinoline zinc (Znq ₂ ), (1,10-phenanthroline) ) -Tris- (4,4,4-Trif Oro-1- (2-thienyl) - butane-1,3-Jioneto) europium _{(III) (Eu (TTA)} 3 (phen)), factory scan (2-phenylpyridine) iridium (Ir _(ppy) 3), Examples include various metal complexes such as 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphine platinum (II).

  Although the average thickness of the light emitting layer 5 is not specifically limited, It is preferable that it is about 10-150 nm, and it is more preferable that it is about 50-100 nm.

  In the display device 10 of the present embodiment as described above, the anode 8 is formed on the inner surface side of the upper substrate 9 (first substrate), and the cathode 3, the electron transport layer 4, and the inner surface side of the TFT circuit substrate 20. After the light emitting layer 5 is formed, the upper substrate 9 and the TFT circuit substrate 20 are joined so that a gap 76 is formed between them, and then a hole transport material is inserted into the gap from the first liquid injection portion 77. The hole transport layer 6 is formed by injecting into the hole 76. By manufacturing the organic EL element 1 using such a method, the hole transport layer 6 is configured not only when it is configured with a solid hole transport material but also with a liquid or semi-solid hole transport material. Therefore, there is an advantage that the range of selection of the hole transport material used for the hole transport layer 6 is widened.

  Hereinafter, a manufacturing method of the display device 10 including a plurality of organic EL elements 1 will be described in detail.

  [1A] First, an upper substrate (first substrate) 9 and a TFT circuit substrate (second substrate) 20 are prepared.

  1A-A: First, the upper substrate 9 is prepared.

  1A-B: Next, a substrate 21 is prepared, and an average thickness of about 200 to 500 nm is formed on the substrate 21 by, for example, plasma CVD using TEOS (tetraethoxysilane) or oxygen gas as a source gas. A base protective layer 23 composed of silicon oxide as a main material is formed.

  1A-C: Next, a driving TFT 24 is formed on the base protective layer 23.

  First, in a state where the substrate 21 is heated to about 350 ° C., a semiconductor film composed mainly of amorphous silicon having an average thickness of about 30 to 70 nm is formed on the base protective layer 23 by, for example, plasma CVD. To do.

  Next, the semiconductor film is crystallized by laser annealing, solid phase growth, or the like to change amorphous silicon into polysilicon.

Here, in the laser annealing method, for example, a line beam with a beam length of 400 mm is used with an excimer laser, and the output intensity is set to about 200 mJ / cm ² , for example. As for the line beam, the line beam is scanned so that a portion corresponding to 90% of the peak value of the laser intensity in the short dimension direction overlaps each region.

  Next, the semiconductor film is patterned to form islands, and an average thickness is formed by, for example, plasma CVD using TEOS (tetraethoxysilane) or oxygen gas as a source gas so as to cover each island-shaped semiconductor film 241. A gate insulating layer 242 composed mainly of silicon oxide or silicon nitride having a thickness of about 60 to 150 nm is formed.

  Next, a conductive film composed mainly of a metal such as aluminum, tantalum, molybdenum, titanium, or tungsten is formed on the gate insulating layer by, for example, sputtering, and then patterned to form the gate electrode 243. .

  Next, in this state, high-concentration phosphorus ions are implanted to form source / drain regions in a self-aligned manner with respect to the gate electrode 243. Note that a portion where no impurity is introduced becomes a channel region.

  1A-D: Next, the source electrode 244 and the drain electrode 245 electrically connected to the driving TFT 24 are formed.

  First, after forming the first interlayer insulating layer 25 so as to cover the gate electrode 243, a contact hole is formed.

  Next, a source electrode 244 and a drain electrode 245 are formed in the contact hole.

  1A-E: Next, a wiring (relay electrode) 27 that electrically connects the drain electrode 245 and the anode 8 is formed.

  First, the second interlayer insulating layer 26 is formed on the first interlayer insulating layer 25, and then contact holes are formed.

  Next, a wiring 27 is formed in the contact hole.

  As described above, the TFT circuit substrate (second substrate) 20 is obtained.

  [2A] Next, the anode 8 is formed on the upper substrate (first substrate) 9.

  The anode 8 is formed by, for example, a vapor deposition method such as sputtering, vacuum deposition, or chemical vapor deposition (CVD), spin coating (pyrosol), casting, or microgravure coating. Liquid phase film forming methods such as gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing, offset printing and ink jet printing. Can be formed.

  These methods are selected in consideration of the physical stability and / or chemical characteristics such as thermal stability of the constituent material of the anode 8 and solubility in a solvent.

  In the present embodiment, since the anode 8 is formed on the entire surface of the upper substrate 9, it is not necessary to use a mask. For this formation, a vapor deposition method such as a vacuum deposition method is preferably used. It is done.

  [3A] Next, as shown in FIG. 3A, on the anode 8, along the outer periphery of the region where the hole transport layer 6 formed in the post-process [11A], that is, the organic EL element 1 is formed, And the 1st protrusion 71 is formed so that a part of the height may become low.

  In the present embodiment, each of the first protrusions 71 has a frame shape (rectangular annular shape), and the height of one side 711 of the four sides of the quadrilateral is lower than the heights of the other sides. To form. At this time, the adjacent first protrusions 71 are integrally formed.

  Specifically, as shown in FIG. 2, wide ridges (ribs) 71a are formed at substantially constant intervals along the x-axis direction so as to be substantially orthogonal to the ridges 71a ( Along the y-axis direction), ridges (ribs) 71b and 71c narrower than the ridge 71a are alternately formed. The height of the ridge 71b is substantially equal to the height of the ridge 71a, and the height of the ridge 71c is lower than the height of the ridge 71a. Further, the ridges 71b and the ridges 71c are formed so that a first pitch and a second pitch narrower than the first pitch are repeated in order.

  With such a configuration, in addition to the inner space (space forming a part of the layer constituting the organic EL element 1) 712 surrounded by the first protrusion 71, the side on the side 711 side of each first protrusion 71 Each part communicates with both the first liquid injection part 77 and the space 712 formed through the upper substrate 9 and the anode 8 in a later step, and serves as a part of the supply path of the hole transport material. A functioning space 713 is formed.

  When the first protrusion 71 and a second protrusion 72 described later are brought into contact with each other, a gap (space) formed between the side 711 and the second protrusion 72 is a second liquid injection part 75. Configure.

  The shape of the space 712, that is, the organic EL element 1 to be formed, may be any shape such as a polygon such as a circle, an ellipse, a triangle, and a hexagon other than the rectangle as in the present embodiment.

  In addition, when making the shape of opening of the 1st protrusion 71 into a polygon, it is preferable that the corner | angular part is rounded. Thereby, the hole transport material can be reliably supplied to every corner of the space inside the first protrusion 71.

  Such a first protrusion 71 can be formed by patterning after forming an insulating film over substantially the entire anode 8.

  The constituent material of the insulating film (first protrusion 71) is selected in consideration of heat resistance, liquid repellency, ink solvent resistance, adhesion to the underlying layer, and the like.

Examples of such materials include organic materials such as acrylic resins and polyimide resins, and inorganic materials such as SiO ₂ .

In particular, when the anode 8 is composed of an oxide material as a main material, it is preferable to use SiO ₂ as a constituent material of the first protrusion 71. Thereby, the adhesion between the anode 8 and the first protrusion 71 can be improved.

  Further, the first protrusion 71 exhibiting liquid repellency can be obtained by, for example, using a fluorine-based resin or performing a fluorine plasma treatment on the surface of the first protrusion 71.

  The thickness of the hole transport layer 6 can be easily controlled by appropriately setting the height of the first protrusion 71.

  Specifically, the height of the first protrusion 71 is preferably about 10 to 150 nm. With this height, the hole transport layer 6 having a desired film thickness can be obtained, and the protrusion obtained by bringing the first protrusion 71 and the second protrusion 72 into contact in the subsequent step [6A]. 7 can sufficiently function as a spacer.

  [4A] Next, as shown in FIG. 3B, the hole transport layer 6 formed in the post-process [11A], that is, the organic EL element 1 is formed on the TFT circuit substrate (second substrate) 20. A second protrusion 72 is formed along the outer periphery of the region.

  In the present embodiment, each of the second protrusions 72 is formed so as to form a frame shape (square ring shape). At this time, the second protrusion 72 is formed so that the upper end portion of the wiring 27 is exposed in the space 722, and the adjacent second protrusions 72 are integrally formed.

  Specifically, as shown in FIG. 2, ridges (ribs) 72a are formed at a substantially constant interval along the x-axis direction, and are substantially orthogonal to the ridges 72a (y-axis direction). Along the above, ridges (ribs) 72b and 71c are formed with a certain distance therebetween. The height of the ridges 72a and the height of the ridges 71b are formed to be substantially equal.

  Such a second protrusion 72 can be formed in the same manner as described for the first protrusion 71.

  The height of the second protrusion 72 is appropriately set according to the total thickness of the cathode 3, the electron transport layer 4 and the light emitting layer 5, and is not particularly limited, but is preferably about 20 to 300 nm. With this height, the protrusion 7 obtained by bringing the first protrusion 71 and the second protrusion 72 into contact with each other in the subsequent step [6A] can sufficiently exhibit the function as a spacer.

  [5A] Next, as shown in FIG. 3C, the cathode 3, the electron transport layer 4 and the light emitting layer 5 are arranged in this order on the TFT circuit substrate (second substrate) 20 exposed inside the space 722. Form with.

  5A-A: First, the cathode (pixel electrode) 3 is formed on the TFT circuit substrate 20 exposed inside each space 722, that is, on the second interlayer insulating layer 26 so as to be in contact with the wiring 27.

  The cathode 3 can be formed by using the vapor phase film forming method or the liquid phase film forming method as described above, and among them, the cathode forming material is supplied using an ink jet method (droplet discharge method). It is preferable to form using an electroless plating method. By using this method, the cathode 3 can be made thinner and the pixel size can be reduced.

  Specifically, the cathode 3 can be formed as follows.

  5A-AI: First, a catalyst is adsorbed on the TFT circuit substrate 20 exposed inside each space 722.

  As the catalyst, one or more of Ni, Cu, Co, Pd, and Pt can be used in combination.

  Among these, when Pd is used as a catalyst, a colloid solution of a Pd alloy such as Sn—Pd or a solution of an ionic Pd catalyst such as palladium chloride is selectively supplied into the space 722 using an ink jet method. As a result, the Pd alloy or the ionic Pd catalyst is adsorbed on the TFT circuit board 20. Then, Pd is exposed on the TFT circuit board 20 by removing elements not involved in the catalyst.

  For example, when using a Sn—Pd colloidal solution, the acid solution is supplied after supplying the colloidal solution onto the TFT circuit substrate 20. As a result, Sn coordinated to Pd is dissolved and removed, and Pd is exposed to the TFT circuit substrate 20.

As the acid solution, for example, a solution containing an acid such as HBF ₄ and a reducing agent such as glucose, or a solution obtained by further adding sulfuric acid to the solution can be used.

  5A-AII: Next, a plating solution mainly composed of a metal salt and a reducing agent is supplied onto the TFT circuit substrate 20 on which the catalyst is adsorbed by using an ink jet method, so that a metal element is deposited in the space 722. Thus, the cathode 3 is formed.

  As the metal salt, for example, sulfate, nitrate and the like are preferably used.

  Examples of the reducing agent include hydrazine, ammonium hypophosphite, sodium hypophosphite, and the like. Among these, those containing at least one of hydrazine and ammonium hypophosphite as a main component are preferable. By using these as the reducing agent, the film forming speed of the cathode 3 becomes appropriate, and the film thickness of the cathode 3 can be controlled relatively easily.

  The content of the metal salt in the plating solution (addition amount of the metal salt to the solvent) is preferably about 1 to 50 g / L, and more preferably about 5 to 25 g / L. If the content of the metal salt is too small, it may take a long time to form the cathode 3. On the other hand, even if the content of the metal salt is increased beyond the upper limit, no further increase in effect can be expected.

  The content of the reducing agent in the plating solution (the amount of the reducing agent added to the solvent) is preferably about 10 to 200 g / L, and more preferably about 50 to 150 g / L. When there is too little content of a reducing agent, there exists a possibility that efficient reduction | restoration of a metal ion may become difficult depending on the kind etc. of reducing agent. On the other hand, even if the content of the reducing agent is increased beyond the upper limit, no further increase in effect can be expected.

  It is preferable to further mix (add) a pH adjusting agent (pH buffering agent) to such a plating solution. As a result, it is possible to prevent or suppress a decrease in the pH of the plating solution with the progress of electroless plating. As a result, it is possible to effectively reduce the deposition rate and change the composition and properties of the cathode 3. Can be prevented.

  Examples of the pH adjuster include various agents, and those having at least one of ammonia water, trimethylammonium hydride, sodium hydroxide, sodium carbonate and ammonium sulfide as a main component are preferable. Since these things are excellent in a buffering effect, the said effect is exhibited more notably by using these things as a pH adjuster.

  5A-B: Next, an electron transport layer 4 is formed on each cathode 3.

  The electron transport layer 4 can be formed by using the vapor phase film formation method or the liquid phase film formation method as described above, and among them, it is preferable to use the ink jet method (droplet discharge method). . By using the inkjet method, the electron transport layer 4 can be made thinner and the pixel size can be reduced. Further, since the liquid electron transport layer forming material can be selectively supplied to the inside of the second protrusion 72, waste of the electron transport material can be omitted.

  Specifically, the material for forming the electron transport layer is discharged from the head of the ink jet printing apparatus, supplied onto each cathode 3, and after removing the solvent or the dispersion medium, if necessary, at about 150 ° C. for a short time. The heat treatment is performed.

  Examples of the desolvent or dedispersion medium include a method of leaving in a reduced pressure atmosphere, a method of heat treatment (for example, about 50 to 60 ° C.), a method of a flow of an inert gas such as nitrogen gas, and the like. Furthermore, the residual solvent is removed by performing additional heat treatment (about 150 ° C. for a short time).

  The electron transport layer forming material to be used is prepared by dissolving or dispersing the electron transport material as described above in a solvent or a dispersion medium.

  Examples of the solvent or dispersion medium used for preparing the electron transport layer forming material include various inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride, and ethylene carbonate, Ketone solvents such as methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), cyclohexanone, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG), glycerin Solvent, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl Ether solvents such as ether (diglyme), diethylene glycol ethyl ether (carbitol), cellosolv solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, toluene, Aromatic hydrocarbon solvents such as xylene and benzene, aromatic heterocyclic solvents such as pyridine, pyrazine, furan, pyrrole, thiophene and methylpyrrolidone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide Amide solvents such as (DMA), halogen compound solvents such as dichloromethane, chloroform, 1,2-dichloroethane, ester solvents such as ethyl acetate, methyl acetate and ethyl formate, sulfur solvents such as dimethyl sulfoxide (DMSO) and sulfolane Compound solvents, nitrile solvents such as acetonitrile, propionitrile, acrylonitrile, various organic solvents such as organic acid solvents such as formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, or mixed solvents containing these It is done.

  The material for forming an electron transport layer supplied on the cathode 3 has high fluidity (low viscosity) and tends to spread in the horizontal direction (plane direction). However, the cathode 3 is surrounded by the second protrusion 72. For this reason, spreading beyond the predetermined region is prevented, and the contour shape of the hole transport layer 6 (organic EL element 1) is accurately defined.

  5A-C: Next, the light emitting layer 5 is formed on each electron transport layer 4 (on the side opposite to the TFT circuit substrate 20 of the cathode 3).

  The light emitting layer 5 can also be formed using a vapor phase film forming method or a liquid phase film forming method, but for the same reason as described above, it is formed using an ink jet method (droplet discharge method). Is preferred. In addition, when the multi-color light emitting layer 5 is provided by using the inkjet method, there is an advantage that the pattern can be easily applied for each color.

  In addition, as shown in FIG. 3C, the light emitting layer 5 is preferably formed to be slightly lower than the height of the second protrusion 72 so as not to protrude from the upper surface of the second protrusion 72. Thereby, in the post-process [11A], the hole transport material can be injected into the gap 76 relatively easily.

  [6A] Next, as shown in FIG. 3D, the first protrusion 71 and the second protrusion 72 are brought into contact with each other so that the space 712 and the space 722 correspond to form the protrusion 7. . As a result, a gap 76 formed by the space 712 and the space 722 is formed between the upper substrate 9 (first substrate) and the TFT circuit substrate 20 (second substrate), and the first protrusions are formed. A second liquid injection part 75 is formed between 71 and the second protrusion 72.

  Further, in the present embodiment, since the first liquid injection part 77 is formed so as to communicate with the space 713 as described above, the second liquid injection part 75, the space 713, and the The first liquid injection portion 77 communicates in this order, and a supply path for injecting the hole transport material into the gap 76 is formed in the post-process [11A].

  In order to make sure that the first protrusion 71 and the second protrusion 72 are in contact with each other, alignment marks (not shown) are formed in advance on both substrates, and the alignment marks are aligned with each other. Therefore, it can be performed relatively easily.

  The second liquid injection part 75 can be formed by lowering the height of a part of the first protrusion 71 as in the present embodiment, and the height of a part of the second protrusion 72 is lowered. It may be formed by reducing the height of a part of both. In addition, the second liquid injection part 75 may be a through hole provided in one of the first protrusion 71 and the second protrusion 72.

  The shape of the second liquid injection part 75 may be any shape such as a semicircle, an ellipse, a triangle, a polygon such as a hexagon, for example, in addition to the quadrangle as in the present embodiment.

  [7A] Next, as shown in FIG. 4A, the upper substrate 9 (first substrate) and the TFT circuit substrate 20 (second substrate) are sealed with a gap 76 at their edges. Bonding is performed by forming the sealing portion 74.

  For example, the sealing portion 74 may be formed of a liquid sealing portion forming material containing an organic material such as an acrylic resin, a polyimide resin, or an epoxy resin or a precursor thereof in a liquid phase such as the ink jet method described above. The film can be formed by supplying it to the region where the sealing portion 74 is formed using a film formation method or the like and then drying it.

  Here, the bonding between the upper substrate 9 and the TFT circuit substrate 20 is a state in which the protrusions 7 are formed by bringing the first protrusions 71 and the second protrusions 72 into contact as described in the above step [6A], that is, It is carried out through a spacer. Thereby, the upper substrate 9 and the TFT circuit substrate 20 can be bonded in a state where the width of the gap 76 formed in the step [6A] with respect to the thickness direction of the upper substrate 9 is substantially constant.

  [8A] Next, by providing a hole in the upper substrate 9 (first substrate) in the thickness direction for each organic EL element 1 to be formed so as not to overlap the region where the light emitting layer 5 is formed. The first liquid injection part 77 is formed.

  In the present embodiment, since the liquid injection part 77 is formed so as to communicate with the space 713, the second liquid injection part 75, the space 713, and the first liquid injection part 77 correspond to each gap 76. Are communicated in this order, and in the subsequent step [11A], a supply path for injecting the hole transport material into the gap 76 is formed.

  As a method of forming the first liquid injection portion 77, that is, a method of removing a part of the upper substrate 9 and forming a hole in the thickness direction, for example, plasma etching, reactive ion etching, beam etching One kind or a combination of two or more kinds of physical etching methods such as photo-assisted etching can be used.

  In the present embodiment, the first liquid injection portion 77 is formed by providing a hole in the upper substrate 9. Thereby, since the first liquid injection part 77 can be formed at a desired position, it is possible to reliably supply (inject) the hole transport material to the position of the target gap 76.

  When the TFT circuit substrate 20 is formed relatively thin, a hole may be provided on the TFT circuit substrate 20 side.

  Further, this hole is provided so as not to overlap with a region where the light emitting layer 5 is formed, that is, a region where the organic EL element 1 is formed. Thereby, it can prevent reliably that the light emission luminance of the organic EL element 1 falls in the area | region in which this hole was provided.

  In the present embodiment, as described above, the hole (first liquid injection portion 77) is formed after the upper substrate 9 and the TFT circuit substrate 20 are joined. With this configuration, the first liquid injection portion 77 can be reliably formed so as to correspond to the position of the formed second liquid injection portion 75. That is, the first liquid injection portion 77 can be formed with higher accuracy in the target region. As a result, the hole transport material supplied so as to close the first liquid injection portion 77 in the subsequent step [11A] is more reliably injected into the gap 76.

  In addition to the holes formed in the order described in this embodiment, the holes may be formed prior to forming a layer other than the hole transport layer, for example. Thereby, it is possible to reliably prevent the influence of heat or the like generated when forming holes in the upper substrate 9 from reaching each layer.

  Further, the hole may be formed, for example, prior to bonding the upper substrate 9 and the TFT circuit substrate 20 after forming a layer other than the hole transport layer. As a result, it is possible to reliably prevent or suppress the removal product generated when the hole is formed in the upper substrate 9 from remaining (attached) in the gap 76. The deterioration of the characteristics of the organic EL element 1 can be surely prevented.

  [9A] Next, the gap 76 is depressurized.

  The method for reducing the pressure of the gap 76 is not particularly limited. For example, the bonding between the upper substrate 9 and the TFT circuit substrate 20 that has undergone the steps [1A] to [8A] in a chamber (not shown) capable of being reduced in pressure. After installing the body, a method of reducing the pressure can be used.

  [10A] Next, as shown in FIG. 5A, the hole transport material is supplied so as to close the first liquid injection part 77 in a state where the gap 76 is decompressed.

  The hole transport material can be supplied to the first liquid injection portion 77 by using the liquid phase film forming method as described above. Among these, the ink jet method (droplet discharge method) is used. It is preferable to supply. By using the ink jet method, the hole transport material can be selectively blocked by the first liquid injection portions 77, so that waste of the hole transport material can be omitted. Further, when the organic EL element 1 including the light emitting layers 5 of a plurality of colors is formed, a hole transport material suitable for the light emitting layer 5 for each color is easily supplied (painted separately) to the first liquid injection portion 77. There is also an advantage that it can.

  Further, when a solid material is used as the hole transport material, by heating the hole transport material to a molten state, various kinds of materials can be used as in the case of using a liquid or semi-solid hole transport material. The hole transport material can be supplied to the first liquid injection portion 77 using a liquid phase film formation method. In addition to these methods, for example, a bulky hole transport material larger than the cross section of the first liquid injection portion 77 can be disposed in the first liquid injection portion 77.

  Note that the hole transport material supplied to the first liquid injection part 77 in a molten state may have solidified by heat dissipation prior to performing the next step [11A], or may maintain the molten state. It may be.

  [11A] Next, as shown in FIG. 5B, the hole transport layer 6 is injected by injecting a hole transport material into the gap 76 by utilizing the difference between the pressure of the gap 76 and the atmospheric pressure. Form.

  This can be performed, for example, by returning the pressure in the chamber in which the joined body of the upper substrate 9 and the TFT circuit substrate 20 is set to atmospheric pressure.

  That is, when the reduced pressure in the chamber is returned to atmospheric pressure, the pressure in the gap 76 becomes lower than the pressure outside the gap 76. As a result, as shown in FIG. 5 (a), a force that restores the pressure in the gap 76 to atmospheric pressure acts, so that the supply path (first liquid injection section) that connects the inside of the gap 76 and the outside of the gap 76 is used. 77, the space 713, and the second liquid injection portion 75), an attractive force is generated from the outside of the gap 76 to the inside of the gap 76. As a result, the hole transport material supplied so as to close the first liquid injection portion 77 is drawn into the gap 76, and as a result, the hole transport layer 6 is formed.

  Here, the protrusion 7 is formed along the outer periphery of the region where the hole transport layer 6 is formed, and the hole transport material injected from the first liquid injection portion 77 is formed on the side surface of the protrusion 7. A second liquid injection part 75 for injecting into the gap 76 via the space 713 is provided. Accordingly, the hole transport material can be injected into the inside of the protrusion 7, that is, into the gap 76, and the protrusion 7 functions as a barrier layer that prevents the hole transport material from flowing out of the gap 76. Therefore, the hole transport layer 6 can be formed corresponding to the shape of each organic EL element 1. That is, the individual hole transport layer 6 can be formed corresponding to each organic EL element 1.

  In the step [7A], the upper substrate 9 and the TFT circuit substrate 20 maintain the substantially constant width of the gap 76 in the thickness direction of the upper substrate 9 through the protrusions (spacers) 7. Are joined. Therefore, in this step, the hole transport layer 6 having a uniform thickness can be obtained by injecting the hole transport material into the gap 76.

  Furthermore, the thickness of the hole transport layer 6 can be set to a desired thickness without being affected by physical properties such as the viscosity of the hole transport material by appropriately setting the height of the protrusion 7.

The pressure difference between the atmospheric pressure and the pressure of the gap 76 may be set so that the hole transport material is injected into the gap 76 and is not particularly limited, but is 1.0 × 10 ⁻⁴ to 1. It is preferably about 0 × 10 ¹² Pa, and more preferably about 1.0 × 10 ^{1 to} 1.0 × 10 ⁵ Pa. When the pressure difference is less than the lower limit, the hole transport material may not be injected into the gap 76 depending on the viscosity of the hole transport material. Further, when the pressure difference is increased beyond the upper limit, gas in the atmosphere other than the hole transport material is injected into the gap 76, and bubbles may be mixed into the hole transport material, which is not preferable.

  Here, when the hole transport material supplied so as to close the first liquid injection part 77 is injected into the gap 76, the hole transport material is supplied from the first liquid injection part 77 to the gap 76. In order to smoothly pass through the passage, the hole transport material needs to be in a liquid or semi-solid state and have a low viscosity.

  Therefore, as a hole transporting material, I: a semi-solid material having a high viscosity at room temperature, II: a molten state (semi-solid material) is maintained after the step [10A]. In the case where a material having a high viscosity, III: a solid material is used, the hole transport material supplied so as to close the first liquid injection portion 77 is injected into the gap 76 before the hole transport material is injected. Need to be heated. Thereby, the viscosity of the semi-solid material is reduced, and the viscosity of the solid material is decreased after being melted in the same manner as the semi-solid material. As a result, the hole transport material whose viscosity has been lowered smoothly passes through the supply path and is injected into the gap 76. Note that these hole transport materials are solidified or increased in viscosity by heat dissipation after being injected into the gap 76 to form the solid or semi-solid hole transport layer 6.

  Such a hole transport material can be heated, for example, by heating one or both of the upper substrate 9 and the TFT circuit substrate 20. Thereby, a hole transport material can be heated and the viscosity of this hole transport material can be reduced reliably.

  Specifically, for example, it can be performed by providing a heating means (not shown) such as a heater on the surface opposite to the upper substrate 9 of the TFT circuit substrate 20.

  In addition, when a liquid or a semi-solid material having a low viscosity is used as the hole transport material, heating of the hole transport material as described above can be omitted, and the hole transport material is injected into the gap 76. The manufacturing cost can be reduced because the time and effort is saved. Since these hole transport materials maintain a liquid or semi-solid state at room temperature even after being injected into the gap 76, the liquid or semi-solid hole transport material 6 is constituted.

  Further, the viscosity of the hole transport material is low, and in the step [10A], the hole transport material supplied so as to close the first liquid injection part 77 has a pressure difference between the atmospheric pressure and the pressure of the gap 76. In the case where it can be injected into the gap 76 without using it, the step [9A] and this step [11A] may be omitted and the hole transport layer 6 may be formed.

  In addition, as a hole transport material, in the case of a low molecule, it is liquid or semi-solid at room temperature. However, when a material that becomes solid by polymerizing is used, the hole transport material is in a low molecular state. The solid hole transport material 6 can be formed by injecting the hole transport material into the gap 76 from the first liquid injection portion 77 and then polymerizing the hole transport material by light irradiation. .

  Moreover, when forming the solid hole transport layer 6 using this hole transport material, it is preferable to add a polymerization initiator to the hole transport material.

  The polymerization initiator is not particularly limited, and examples thereof include a photopolymerization initiator such as a photo radical polymerization initiator and a photo cationic polymerization initiator. Examples of the polymerizable group provided in the hole transport material include: When a (meth) acryloyl group and a vinyl benzyl ether group are used, it is preferable to use a photo radical polymerization initiator. For example, when an epoxy group, an oxetane group, a vinyl ether group or the like is used, a photo cationic polymerization initiator is used. Is preferably used.

  As the radical photopolymerization initiator, various radical photopolymerization initiators can be used. For example, benzophenone, benzoin, acetophenone, benziketal, Michler's ketone, acylphosphine oxide, ketocoumarin, xanthene In addition, photo radical polymerization initiators such as thioxanthone can be used.

  As the cationic photopolymerization initiator, various kinds of cationic photopolymerization initiators can be used. For example, aromatic sulfonium salt type, aromatic iodonium salt type, aromatic diazonium salt type, pyridium salt type and aromatic phosphonium salt. An onium salt-based photocationic polymerization initiator such as a non-ionic photocationic polymerization initiator such as an iron arene complex or a sulfonic acid ester can be used.

  Examples of the light to be irradiated include infrared rays, visible rays, ultraviolet rays, and X-rays, and one or two or more of these can be used in combination. Among them, particularly, ultraviolet rays are used. Is preferred. Thereby, the polymerization reaction between the compounds can easily and reliably proceed.

  Further, as shown in FIG. 1, almost all of the hole transport material may be present in the gap 76, but a part of the hole transport material is present in the second liquid injection part 75 or the space 713. It may be like that. Selection of the position and amount of the hole transport material can be easily performed by adjusting the supply amount and viscosity of the hole transport material.

  [12A] Next, as shown in FIG. 5C, the first liquid injection portion 77 is sealed.

  Sealing of the first liquid injection portion 77 can be performed, for example, in the same manner as forming the sealing portion 74 using the sealing portion forming material described in the step [7A].

  Through the steps as described above, the display device 10 including a plurality of organic EL elements 1 can be formed.

  In the present embodiment, the anode 8 is formed on the upper substrate (first substrate) 9 side, and the cathode 3, the electron transport layer 4 and the light emitting layer 5 are formed on the TFT circuit substrate (second substrate) 20 side. Although described above, the present invention is not limited to this. For example, the cathode 3, the electron transport layer 4 and the light emitting layer 5 are provided on the upper substrate (first substrate) 9 side, and the TFT circuit substrate (second substrate) 20 side is provided. Alternatively, the anode 8 may be formed.

  Further, the anode 8 is individually formed so as to correspond to each organic EL element 1 similarly to the cathode 3, in addition to the case where it is a common electrode, that is, integrally formed as in the present embodiment. It may be a thing.

  Moreover, although this embodiment demonstrated the case where the positive hole transport layer 6 was formed separately corresponding to each organic EL element 1, it is not limited to such a case, For example, several organic EL element 1 is provided. A common hole transport layer 6 may be formed.

  Such a hole transport layer 6 is, for example, a first corresponding to the organic EL element 1 that forms the common hole transport layer 6 so that the hole transport material can be supplied to both the adjacent gaps 76. The protrusion 71b of the protrusion 71 can be obtained in the same manner as the height of the protrusion 71c.

Second Embodiment
Next, a second embodiment of an active matrix display device to which the organic light emitting device of the present invention is applied will be described.

  6 to 8 are views showing a second embodiment of an active matrix display device to which the organic light emitting device of the present invention is applied. FIG. 6 is a longitudinal sectional view, FIG. 7 is a perspective view, and FIG. FIG. 9 to 11 are views for explaining a method of manufacturing the active matrix display device shown in FIGS. In FIG. 7, for the convenience of explanation, the display device is shown upside down with respect to the display device of FIG. In the following description, the upper side in FIGS. 6 and 9 to 11 is referred to as “upper”, and the lower side is referred to as “lower”.

  Hereinafter, the second embodiment will be described with a focus on differences from the first embodiment, and description of similar matters will be omitted.

  In the display device 10 shown in FIGS. 6 to 8, the upper substrate 9 is composed of a base substrate 91 and a resin layer 92, and a liquid repellent treatment is performed on the surface of the upper substrate 9. 9 except that the first liquid injection part 77 provided in the first hole 771 is composed of a first hole 771 and a second hole 772 smaller than the cross section of the first hole 771. This is the same as the display device 10. Since the periphery of the upper substrate 9 where the first liquid injection part 77 is formed is subjected to a liquid repellent treatment, the hole transport material supplied to the first liquid injection part 77 is used as the upper substrate 9. As a result, it is possible to reliably prevent the surface from getting wet and spread, and as a result, the hole transport material can be reliably injected into the gap 76 from the first liquid injection portion 77. Further, by providing the first hole 771 having a larger cross-sectional area than the second hole 772 on the upper side, the hole transport material can be stored in the first hole 771.

  Similar to the first embodiment, the upper substrate 9 functions as a protective layer for protecting the organic light emitting element 1. In this embodiment, the upper substrate 9 is provided on the base substrate 91. And a resin layer 92.

  As a constituent material of the base substrate 91, in addition to various glass material substrates and various high-hardness resin substrates, for example, carbon materials such as ceramic materials, metal materials, carbon fibers, and the like can be used.

  Examples of the constituent material of the resin layer 92 include a polyimide resin, a polyester resin, a polyamide resin, a polyether resin such as polyether ether ketone and polyether sulfone. Among these, since the polyimide-based resin has a small coefficient of thermal expansion and thermal contraction, the thermal contraction rate of the resin layer 92 can be kept low by configuring the resin layer 92 using the polyimide-based resin as a main material. . In addition, there is an advantage that the liquid repellency can be imparted to the upper surface of the resin layer 92 relatively easily by the liquid repellency treatment performed in the step [4B] described in the method for manufacturing the display device 10.

  Furthermore, the shrinkage rate of the resin layer 92 can be reduced and the dimensional stability can be improved by laminating fillers and fibers in such a resin material, or by adjusting the pre-heat treatment and the degree of crosslinking. .

  The average thickness of the base substrate 91 is not particularly limited, but is preferably about 0.1 to 30 mm, and more preferably about 0.5 to 2.0 mm. Further, the thickness of the resin layer 92 is not particularly limited, but is preferably about 1 to 100 μm, and more preferably about 10 to 30 μm.

  Next, a manufacturing method of the display device 10 of the present embodiment including the upper substrate 9 having the above-described configuration will be described in detail.

  [1B] First, an upper substrate (first substrate) 9 and a TFT circuit substrate (second substrate) 20 are prepared.

  1B-A: First, a base substrate 91 is prepared, and a liquid resin layer forming material containing the above-described resin material or its precursor is supplied (applied) onto the base substrate 91 and dried. The resin layer 92 is formed by solidifying and curing. Thereby, the upper substrate (first substrate) 9 provided with the resin layer 92 on the base substrate 91 is obtained.

  The supply of the resin layer forming material onto the base substrate 91 can be performed using the liquid phase film forming method described in the above step [2A], and the solvent used when preparing the resin layer forming material. Or as a dispersing agent, the thing similar to what was demonstrated at the said process [5A] can be used.

  1B-B: Next, a TFT circuit substrate (second substrate) 20 is obtained in the same manner as in Steps 1A-B to 1A-E.

  [2B] Next, the anode 8 is formed on the surface of the upper substrate (first substrate) 9 opposite to the resin layer 92 in the same manner as in the step [2A].

  [3B] Next, as shown in FIG. 9A, the hole transport layer 6 formed in the post-process [12B], that is, the organic EL element 1 is formed on the anode 8 in the same manner as in the process [3A]. The first protrusion 71 is formed along the outer peripheral portion of the region to be formed and so that a part of the height is lowered.

  [4B] Next, as shown in FIG. 9B, a liquid repellent treatment is performed on the surface of the upper substrate (first substrate) 9 on the resin layer 92 side.

  As this liquid repellent treatment, for example, a method of forming a liquid repellent film by supplying a liquid repellent material to the upper surface of the resin layer 92, a fluorine plasma treatment method of irradiating fluorine plasma, or the like is used. Among these, it is preferable to use a fluorine plasma treatment method.

  In this fluorine plasma processing method, a fluorine-containing gas is introduced into a discharge region that generates fluorine plasma, and the fluorine plasma generated in this discharge region is incident on the upper surface of the resin layer 92, so that the fluorine plasma is incident. Liquid repellency is imparted to the formed region.

  According to such a processing method, the upper surface of the resin layer 92 can be uniformly fluorinated almost entirely, that is, the liquid repellent property can be imparted uniformly (evenly) to the upper surface of the resin layer 92.

Examples of the gas species containing a fluorine atom include tetrafluoromethane (CF ₄ ), tetrafluoroethylene (C ₂ F ₄ ), hexafluoropropylene (C ₃ F ₆ ), and octafluorobutylene (C _4). F ₈ ) and the like, and among these, those mainly containing tetrafluoromethane are preferred.

  The flow rate of the gas containing fluorine atoms is preferably about 10 to 500 sccm, and more preferably about 50 to 400 sccm.

The RF power is preferably about 0.005 to 0.2 W / cm ² , and more preferably about 0.05 to 0.1 W / cm ² .

  In addition, it is preferable that the pressure in this case is under atmospheric pressure. Thereby, use of a chamber, a decompression means, etc. can be made unnecessary, and it can process at low energy and low cost.

  The liquid repellent treatment may be performed over almost the entire surface of the resin layer 92 as in this embodiment, or the first liquid injection portion 77 (first step) formed in the next step [5B]. It may be applied locally so as to surround a region where one hole 771) is provided. Even when the liquid repellent treatment is performed on such a region, it is possible to reliably impart liquid repellency to the region surrounding at least the first liquid injection portion 77 on the upper surface of the upper substrate 9, that is, the upper surface of the resin layer 92. .

  [5B] Next, the first liquid is injected in the thickness direction for each organic EL element 1 to be formed so as not to overlap the region where the light emitting layer 5 is formed on the upper substrate 9 (first substrate). A portion 77 is formed.

  In the present embodiment, as shown in FIGS. 8 and 10, the first liquid injection portion 77 includes a first hole 771 and a second hole 772. The cross section of the second hole 772 is smaller than the cross section of the first hole 771, and the second hole 772 connects the first hole 771 and the space 713 formed in the post-process [8B]. By using the first liquid injection portion 77 having such a configuration, the hole transport material supplied so as to close the first liquid injection portion 77 in the subsequent step [11B] Can be held (stored).

  In the present embodiment, the first hole 771 and the second hole 772 have a circular cross section as shown in FIG. 8, but are not limited to such a shape. Any shape such as a polygon, such as a shape, a triangle, a quadrangle, and a hexagon may be used.

  A method for forming such a first liquid injection portion 77 is not particularly limited, and examples thereof include the following.

  First, as shown in FIG. 9C, a part of the resin layer 92 and the base substrate 91 is removed in the thickness direction of the upper substrate 9 so that the cross section of the first hole 771 to be formed later is larger. A second hole 772 is formed to be small. In the present embodiment, the second hole 772 is formed so as to communicate with the space 713.

  Next, as shown in FIG. 9D, a part of the resin layer 92 is removed in the thickness direction of the upper substrate 9 so as to communicate with the second hole 772 formed earlier, A first hole 771 larger than the cross section of the second hole 772 is formed. Thereby, the first liquid injection part 77 constituted by the first hole 771 and the second hole 772 can be obtained.

  Note that in the case where a relatively large amount of hole transport material needs to be stored in the first hole 771, the first hole 771 is a base substrate so that the second hole 772 remains in addition to the resin layer 92. It may be formed by removing a part of 91 in the thickness direction of the upper substrate 9.

  As a method of forming the first hole 771 and the second hole 772, that is, a method of removing a part of the base substrate 91 and the resin layer 92, for example, the physical etching method described in the step [8A] is used. One kind or a combination of two or more kinds can be used.

  In addition, a lyophilic process may be performed inside the first liquid injection unit 77. Thereby, the lyophilicity inside the first liquid injection part 77 (particularly, the first hole 771) can be improved, so that the first liquid injection part 77 is blocked in the post-process [11B]. The hole transport material supplied to the first hole 771 can be reliably held in the first hole 771.

  As this lyophilic treatment, for example, a method of irradiating the inside of the first liquid injection part 77 with ultraviolet rays and / or infrared rays in an oxygen-containing atmosphere, or an oxygen plasma treatment method of irradiating oxygen plasma is used. Among these, it is preferable to use an oxygen plasma treatment method.

  In this oxygen plasma treatment method, a gas containing oxygen is introduced into a discharge region where oxygen plasma is generated, and the oxygen plasma generated in this discharge region is made incident on the inside of the first liquid injection portion 77, whereby It imparts liquidity.

  According to this processing method, lyophilicity can be easily and reliably imparted to the inside of the first liquid injection portion 77, particularly to the inside of the first hole 771.

  As the gas containing oxygen gas, pure oxygen gas is typically used, but a mixed gas of oxygen gas and fluorocarbon gas (for example, tetrafluoromethane gas) is preferably used. Thereby, the time during which the oxygen plasma is maintained is lengthened, and the inside of the first liquid injection portion 77 can be reliably reached in the state of oxygen plasma.

  The oxygen gas concentration (content ratio) in this mixed gas is preferably about 60 to 90 vol%, more preferably about 65 to 80 vol%.

  By setting the concentration of the oxygen gas within the above range, the oxygen plasma can be made to reach the inside of the first liquid injection portion 77 more efficiently.

  The flow rate of the gas containing oxygen gas is preferably about 10 to 500 sccm, and more preferably about 50 to 400 sccm.

Also, RF power is preferably in the range of about 0.005~0.2W / cm ^2, more preferably about 0.05~0.1W / cm ^2.

  The pressure at this time is preferably under atmospheric pressure. Thereby, use of a chamber, a decompression means, etc. can be made unnecessary, and it can process at low energy and low cost.

  The first liquid injection portion 77 is provided so as not to overlap with a region where the light emitting layer 5 is formed, that is, a region where the organic EL element 1 is formed. Thereby, it is possible to reliably prevent the light emission luminance of the organic EL element 1 from being lowered in the region where the first liquid injection part 77 is provided.

  In the present embodiment, as described above, the first liquid injection portion 77 is formed prior to the formation of the electron transport layer 4 and the light emitting layer 5 other than the hole transport layer 6. With such a configuration, it is possible to reliably prevent the influence of heat and the like generated when the first liquid injection portion 77 is formed on the upper substrate 9 from reaching each layer.

  Further, the hole (first liquid injection portion 77) is formed in the process as described in the present embodiment, for example, after the upper substrate 9 and the TFT circuit substrate 20 are joined. May be. Thereby, a hole can be reliably formed so as to correspond to the position of the liquid injection part formed in the post-process [8B]. That is, the hole can be formed with higher accuracy in the intended region. As a result, the hole transport material supplied so as to close the first liquid injection portion 77 in the post-process [12B] can be more reliably injected into the gap.

  Further, the hole may be formed, for example, prior to bonding the upper substrate 9 and the TFT circuit substrate 20 after forming a layer other than the hole transport layer. As a result, it is possible to reliably prevent or suppress the removal product generated when the hole is formed in the upper substrate 9 from remaining (attached) in the gap 76. The deterioration of the characteristics of the organic EL element 1 can be surely prevented.

  When the TFT circuit substrate 20 is formed relatively thin, such a hole may be provided on the TFT circuit substrate 20 side.

  Further, the first liquid injection part 77 is configured by the first hole 771 and the second hole 772 as in the present embodiment, and for example, the first hole 771 is not formed. In other words, the second hole 772 may be configured as shown in FIG. In this case, a lyophilic process may be performed on a region corresponding to the omitted first hole 771 in the upper surface of the resin layer 92, and a liquid repellent process may be performed so as to surround the region.

  [6B] Next, in the same manner as in the above step [4A], as shown in FIG. 10A, hole transport formed in the post step [12B] on the TFT circuit substrate (second substrate) 20 is performed. A second protrusion 72 is formed along the outer periphery of the region 6 where the organic EL element 1 is to be formed.

  [7B] Next, in the same manner as in the above step [5A], as shown in FIG. 10B, the cathode 3 and the electrons are formed on the TFT circuit substrate (second substrate) 20 exposed inside the space 722. The transport layer 4 and the light emitting layer 5 are formed in this order.

  [8B] Next, in the same manner as in the above step [6A], as shown in FIG. 10C, the first protrusion 71 and the second protrusion 72 are made to correspond to the space 712 and the space 722. Then, the projection 7 is formed in contact with each other. As a result, a gap 76 formed by the space 712 and the space 722 is formed between the upper substrate 9 (first substrate) and the TFT circuit substrate 20 (second substrate), and the first protrusions are formed. A second liquid injection part 75 is formed between 71 and the second protrusion 72.

  [9B] Next, in the same manner as in the above step [7A], as shown in FIG. 10D, the upper substrate 9 (first substrate) and the TFT circuit substrate 20 (second substrate) are separated from each other. Bonding is performed by forming a sealing portion 74 that seals the gap 76 at the edge portion of the first portion.

  [10B] Next, the gap 76 is decompressed in the same manner as in the step [9A].

  [11B] Next, in the same manner as in the above step [10A], as shown in FIG. 11A, hole transport is performed so as to block the first liquid injection portion 77 in a state where the gap 76 is decompressed. Supply material.

  Here, in the present embodiment, as described above, the first liquid injecting portion 77 connects the first hole 771, the first hole 771, and the space 713, and the cross section of the first hole 771. The second hole 772 is smaller than the second hole 772. Therefore, the hole transport material supplied to the first liquid injection part 77 can be reliably held (stored) in the first hole 771.

  Further, as shown in FIG. 11A, even when the hole transport material is supplied so as to fill the first hole 771, in the method for manufacturing an organic light emitting device of the present invention, the upper substrate (first Since the liquid repellent treatment is applied to the upper surface of the substrate 9, that is, the upper surface of the resin layer 92 in this embodiment, the liquid repellency of the resin layer 92 with respect to the hole transport material is the first hole 771. It is higher than the liquid repellency of the inner surface. Therefore, the hole transport material is prevented from moving to the upper surface of the resin layer 92. Accordingly, the hole transport materials supplied to the adjacent first liquid injection portions 77 are reliably prevented from being mixed on the resin layer 92, and Can be reliably held (stored) in the region where the hole 771 is formed. As a result, the hole transport material can be reliably transferred into the gap 76 in the next step [12B]. Such a configuration includes a light emitting layer 5 composed of different light emitting materials between adjacent organic EL elements 1, and a hole transport material suitable for these light emitting layers 5 is used for each organic EL element 1. It is particularly effective.

  Further, since the first hole 771 is provided, even if a droplet of the hole transport material is supplied to a position away from the second hole 772, the droplet is caused to flow by the first hole 771. It is possible to store the hole transport material in the first hole 711 so as to block the second hole 772 by restricting wetting and spreading. As a result, in the next step [12B], since the hole transport material can be injected into the gap 76 without leaving the hole transport material on the resin layer 92, the injection efficiency of the hole transport material can be improved. it can.

  Further, the difference in the degree of liquid repellency between the upper surface of the resin layer 92 and the inner surface of the first hole 771 (first liquid injection portion 77) can be expressed by various indicators, but the contact angle is used. And can be suitably expressed.

  Specifically, when the contact angle of the hole transport material on the upper surface of the resin layer 92 is A [°] and the contact angle of the hole transport material in the first hole 771 is B [°], A It is preferable to satisfy the relationship of −B ≧ 15 °, and it is more preferable to satisfy the relationship of AB ≧ 30 °. Even if the hole transport material is supplied so as to be thicker than the thickness of the resin layer 92 (first hole 771), that is, to fill the first hole 771, by satisfying such a relationship. Further, diffusion (migration) to the upper surface of the resin layer 92 can be more reliably prevented.

  The hole transport material can be supplied to the first liquid injection portion 77 by using the liquid phase film forming method as described above. Among these, the ink jet method (droplet discharge method) is used. It is preferable to supply. According to the ink jet method, the hole transport material can be reliably supplied to the inner surface of the first hole 771, and the diffusion to the resin layer 92 can be more reliably prevented. Further, when the organic EL element 1 including the light emitting layers 5 of a plurality of colors is formed, a hole transport material suitable for the light emitting layer 5 for each color is easily supplied (painted separately) to the first liquid injection portion 77. There is also an advantage that it can.

  Further, when a solid material is used as the hole transport material, by heating the hole transport material to a molten state, various kinds of materials can be used as in the case of using a liquid or semi-solid hole transport material. By using the liquid phase film forming method, the hole transport material in a molten state can be supplied to the first liquid injection portion 77. In addition to these methods, for example, a massive hole transport material larger than the cross section of the second hole 772 may be disposed in the first liquid injection portion 77 (in the first hole 771). It can be carried out.

  Note that the hole transport material supplied to the first liquid injection unit 77 in a molten state may be solidified by heat radiation before the next step [12B] is performed, or the molten state is maintained. It may be.

  [12B] Next, in the same manner as in the above-mentioned step [11A], as shown in FIG. 11B, the hole transport material is removed from the gap 76 by utilizing the difference in pressure between the gap 76 and the atmospheric pressure. Hole transport layer 6 is formed.

  [13B] Next, as in the step [12A], the first liquid injection section 77 is sealed as shown in FIG.

  Through the steps as described above, the display device 10 that has been subjected to the liquid repellent treatment on the surface of the upper substrate 9 can be formed.

  When it is necessary to inject a relatively large number of hole transport materials into the gap 76, a case where one first liquid injection portion 77 is provided corresponding to one gap 76 as in the present embodiment. Without being limited thereto, a plurality of first liquid injection portions 77 may be provided corresponding to one gap 76.

<Third Embodiment>
Next, a third embodiment of an active matrix display device to which the organic light emitting device of the present invention is applied will be described.

  FIG. 12 is a longitudinal sectional view showing a third embodiment of an active matrix display device to which the organic light emitting device of the present invention is applied. In the following description, the upper side in FIG. 12 is referred to as “upper” and the lower side is referred to as “lower”.

  Hereinafter, the third embodiment will be described with a focus on differences from the first embodiment, and description of similar matters will be omitted.

  In the display device 10 shown in FIG. 12, the electron transport layer 4 is formed by injecting an electron transport material into the gap from the first liquid injection part 77 instead of the hole transport layer 6, and the third liquid injection part is formed. Except for being provided so as to correspond to the electron transport layer 4, it is the same as the display device 10 of the first embodiment.

  Examples of the electron transport material constituting the electron transport layer 4 include those that are solid at room temperature and those that are liquid or semi-solid at room temperature, as with the hole transport material described above.

  Here, examples of the electron transport material that is solid at room temperature include those described in the first embodiment. In addition, as the electron transport material that is liquid or semi-solid at room temperature, similarly to the hole transport material, the electron transport material that is solid at room temperature is provided as an electron transport part, and at least connected to the electron transport part. Those having one linear alkyl group are preferably used. By introducing a linear alkyl group into the electron transport portion, that is, a solid electron transport material, the melting point and the glass transition temperature can be lowered without reducing the electron transport capability of the electron transport portion.

  Specifically, examples of the electron transport material that is liquid or semi-solid at room temperature include compounds represented by the following general formula (A2) to general formula (A4).

[In each formula, X ¹ , X ² and X ³ each independently represent a hydrogen atom or a linear alkyl group, and may be the same or different. However, at least one of X ¹ , X ² and X ³ represents a linear alkyl group having 3 to 8 carbon atoms, and the other represents a hydrogen atom, a methyl group or an ethyl group. ]
Such compounds (A2) to (A4) have an excellent electron transport ability and are in a liquid or semi-solid form at room temperature.

  In the present invention, as in the case of the hole transport material, the electron transport material is liquid or semi-solid at room temperature when it is a low molecule (monomer or oligomer). It is also possible to use those that become solid by polymerizing. If such an electron transport material is used, when the electron transport layer 4 is formed in the method for manufacturing the light emitting device 10 to be described later, the electron transport material is used in the liquid or semi-solid (low molecule) state as the first liquid. By injecting into the gap 76 from the injection portion 77 and polymerizing (curing) the electron transport material, the solid electron transport layer 4 can be formed in the gap 76. As described above, by polymerizing the electron transport material, the heat resistance of the electron transport material can be improved. Furthermore, the diffusion of the electron transport material (low molecule) into the light emitting layer 5 can be suitably prevented.

  Such an electron transport material is not particularly limited. For example, a material having a polymerizable group at the terminal of a linear alkyl group of a liquid or semi-solid electron transport material at room temperature as described above is preferably used. It is done.

  As the polymerizable group, the same groups as those described for the polymerizable group provided in the hole transport material can be used.

  As a constituent material (hole transport material) of the hole transport layer 6, for example, in addition to the low-molecular compounds mentioned in the hole transport portion described above, a polymer having an arylamine skeleton such as polyarylamine, fluorene -A polymer having a fluorene skeleton such as a bithiophene copolymer, a polymer having both an arylamine skeleton and a fluorene skeleton such as a fluorene-arylamine copolymer, poly (N-vinylcarbazole), polyvinylpyrene, polyvinyl High molecular compounds such as anthracene, polythiophene, polyalkylthiophene, polyhexylthiophene, poly (p-phenylene vinylene), polytinylene vinylene, pyrene formaldehyde resin, ethyl carbazole formaldehyde resin or derivatives thereof can be given.

  In the display device 10 of this embodiment, the anode 8, the hole transport layer 6 and the light emitting layer 5 are formed on the inner surface side of the upper substrate 9 (first substrate), and the cathode 3 is formed on the inner surface side of the TFT circuit substrate 20. Then, the upper substrate 9 and the TFT circuit substrate 20 are joined so that a gap 76 is formed between them, and then an electron transport material is injected into the gap 76 to form the electron transport layer 4. It is manufactured by.

  Hereinafter, the manufacturing method of the display device 10 according to the third embodiment will be described with respect to differences from the first embodiment.

  First, in the step [3A], the first protrusion 71 is formed according to the total thickness of the hole transport layer 6 and the light emitting layer 5.

  Next, in the step [4A], the third protrusion 72 is formed according to the total thickness of the cathode 3 and the electron transport layer 4.

  Next, in the step [5A], the cathode 3 is formed on the TFT circuit substrate (third substrate) 20 exposed inside the space 722, and the holes are formed on the anode 8 exposed inside the space 712. The transport layer 6 and the light emitting layer 5 are formed in this order.

  Accordingly, in the step [6A], when the first protrusion 71 and the third protrusion 72 are brought into contact with each other to form the protrusion 7, the gap 76 and the position corresponding to the position where the electron transport layer 4 is formed are formed. A third liquid injection part 75 is formed.

  Then, in the step [10A], an electron transport material is supplied so as to block the first liquid injection portion 77, and in the step [11A], the difference between the pressure of the gap 76 and the atmospheric pressure is used. By injecting the electron transport material into the gap 76, the electron transport layer 4 can be formed in the gap 76.

<Fourth embodiment>
Next, a fourth embodiment of an active matrix display device to which the organic light emitting device of the present invention is applied will be described.

  FIG. 13 is a longitudinal sectional view showing a fourth embodiment of an active matrix display device to which the organic light emitting device of the present invention is applied. In the following description, the upper side in FIG. 13 is referred to as “upper” and the lower side is referred to as “lower”.

  Hereinafter, the fourth embodiment will be described with a focus on differences from the first embodiment, and description of similar matters will be omitted.

  In the display device 10 shown in FIG. 13, particles 78 are used as spacers instead of the protrusions 7, and the hole transport layer 6 is integrally provided, that is, common to all the organic EL elements 1. This is the same as the display device 10 of the first embodiment. Even when the particles 78 are used as the spacers, the gap thickness can be easily and reliably controlled as in the case where the protrusions 7 are used.

  In the present embodiment, the sealing portion 74 functions as a barrier layer that prevents the hole transport material from flowing out of the organic EL element 1.

  Such a display device 10 of this embodiment can be manufactured by changing the manufacturing method described in the display device 10 of the first embodiment as follows.

  First, the formation of the first protrusion 71 in the step [3A] and the formation of the second protrusion 72 in the step [4A] are omitted.

  Next, in forming the gap between the upper substrate 9 and the TFT circuit substrate 20 in the step [6A], particles 78 are interposed (arranged) between the anode 8 and the light emitting layer 5. Thereby, the function as a spacer can be exerted on the particles 78, and the width of the formed gap with respect to the thickness direction of the upper substrate 9 can be made substantially constant.

  The average particle diameter of the particles 78 is appropriately set according to the thickness of the hole transport layer 6 and is not particularly limited, but is preferably about 10 to 150 nm. Thereby, the function as a spacer which can obtain the thickness of the target positive hole transport layer 6 to the particle | grain 78 can be exhibited reliably.

  The constituent material of such particles 78 is not particularly limited, but for example, the same material as described for the constituent material of the first protrusion 71 is preferably used. Thereby, it can prevent or suppress that the injection | pouring efficiency of the hole to the light emitting layer 5 of the hole transport layer 6 reduces.

  Then, in the step [11A], the hole transport layer 6 is integrally formed by injecting the hole transport material over almost the entire gap by utilizing the difference between the pressure of the gap and the atmospheric pressure. Can be formed.

  Note that the hole transport material may be injected from the side of the space 713 instead of being injected from the first liquid injection portion 77.

  As described above, according to the method for manufacturing an organic light-emitting device of the present invention, the carrier (for example, hole or electron) transport layer formed by injecting into the gap formed between the substrates forms the laminate. It will be formed at the end of the process for the other layers that make up. Therefore, each organic EL element (each pixel) 1 is formed as a result of forming the light-emitting layer or other carrier transport layer formed by the liquid phase film forming method or the gas phase film forming method so that the characteristics are suitably exhibited. Even in the case where variations occur in the thicknesses of the layers, by injecting the carrier transport material into the gap, the variations can be eliminated and the thicknesses of the layers as a laminate can be made uniform. .

  Therefore, it is preferable to apply the carrier transport layer formed by injecting into the gap to a layer whose thickness does not relatively affect the characteristics of the organic EL element. From this viewpoint, it is preferable to apply the carrier transport layer formed by injecting into the gap to the hole transport layer.

  As described above, in the first embodiment, the second embodiment, and the fourth embodiment, the carrier transport layer formed by injecting a predetermined carrier transport material into the gap 76 from the first liquid injection portion 77 is the positive In the third embodiment, the case where the hole transport layer is applied to the electron transport layer has been described. However, the present invention is not limited to such a case. For example, the organic EL element 1 includes a plurality of hole transport layers and electron transport layers. The organic light-emitting device manufacturing method of the present invention is applied to the formation of these layers. May be.

<Electronic equipment>
Such a display device (organic light-emitting device of the present invention) 10 can be incorporated into various electronic devices.

  FIG. 14 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which the electronic apparatus of the present invention is applied.

  In this figure, a personal computer 1100 includes a main body 1104 provided with a keyboard 1102 and a display unit 1106 provided with a display. The display unit 1106 is rotatable with respect to the main body 1104 via a hinge structure. It is supported by.

  In the personal computer 1100, the display unit included in the display unit 1106 is configured by the display device 10 described above.

  FIG. 15 is a perspective view showing a configuration of a mobile phone (including PHS) to which the electronic apparatus of the invention is applied.

  In this figure, a cellular phone 1200 includes a plurality of operation buttons 1202, an earpiece 1204 and a mouthpiece 1206, and a display unit.

  In the mobile phone 1200, the display unit is configured by the display device 10 described above.

  FIG. 16 is a perspective view showing a configuration of a digital still camera to which the electronic apparatus of the present invention is applied. In this figure, connection with an external device is also simply shown.

  Here, an ordinary camera sensitizes a silver halide photographic film with a light image of a subject, whereas a digital still camera 1300 photoelectrically converts a light image of a subject with an imaging device such as a CCD (Charge Coupled Device). An imaging signal (image signal) is generated.

  A display unit is provided on the back of a case (body) 1302 in the digital still camera 1300, and is configured to display based on an imaging signal from the CCD, and functions as a finder that displays an object as an electronic image.

  In the digital still camera 1300, the display unit is configured by the display device 10 described above.

  A circuit board 1308 is installed inside the case. The circuit board 1308 is provided with a memory that can store (store) an imaging signal.

  A light receiving unit 1304 including an optical lens (imaging optical system), a CCD, and the like is provided on the front side of the case 1302 (on the back side in the illustrated configuration).

  When the photographer confirms the subject image displayed on the display unit and presses the shutter button 1306, the CCD image pickup signal at that time is transferred and stored in the memory of the circuit board 1308.

  In the digital still camera 1300, a video signal output terminal 1312 and an input / output terminal 1314 for data communication are provided on the side surface of the case 1302. As shown in the figure, a television monitor 1430 is connected to the video signal output terminal 1312 and a personal computer 1440 is connected to the input / output terminal 1314 for data communication as necessary. Further, the imaging signal stored in the memory of the circuit board 1308 is output to the television monitor 1430 or the personal computer 1440 by a predetermined operation.

  In addition to the personal computer (mobile personal computer) in FIG. 14, the mobile phone in FIG. 15, and the digital still camera in FIG. 16, the electronic apparatus of the present invention includes, for example, a television, a video camera, a viewfinder type, Monitor direct-view video tape recorder, laptop personal computer, car navigation system, pager, electronic notebook (including communication function), electronic dictionary, calculator, electronic game device, word processor, workstation, videophone, security TV Monitors, electronic binoculars, POS terminals, devices with touch panels (for example, cash dispensers of financial institutions, automatic ticket vending machines), medical devices (for example, electronic thermometers, blood pressure monitors, blood glucose meters, electrocardiographs, ultrasound diagnostic devices, internal Endoscopic display device), fish finder, various measurements Vessels, instruments (e.g., gages for vehicles, aircraft, and ships), a flight simulator, various monitors, and a projection display such as a projector.

  As mentioned above, although the manufacturing method of the organic light-emitting device, organic light-emitting device, and electronic device of this invention were demonstrated based on embodiment of illustration, this invention is not limited to these.

  For example, in the method for manufacturing an organic light-emitting device of the present invention, one or two or more optional steps may be added.

  Moreover, the organic light-emitting device of the present invention may be a combination of any two or more configurations (features) of the above-described embodiments.

  Furthermore, the structure of each part of the organic light-emitting device of the present invention can be replaced with an arbitrary one that can exhibit the same function, or an arbitrary structure can be added.

  Next, specific examples of the present invention will be described.

1. Synthesis of Compound First, a compound (A) as shown below was prepared.

<Compound (A)>
1 mol of 4-hexylaniline was dissolved in 150 mL of acetic acid, and acetic anhydride was added dropwise at room temperature, followed by stirring. After completion of the reaction, the precipitated solid was filtered, washed with water and dried.

  Next, 0.37 mol of the obtained substance, 0.66 mol of 1-bromo-4-hexylbenzene, 1.1 mol of potassium carbonate, copper powder and iodine were mixed and heated at 200 ° C. After standing to cool, 130 mL of isoamyl alcohol, 50 mL of pure water, and 0.73 mol of potassium hydroxide were added and the mixture was stirred and dried.

  Further, 130 mmol of the compound obtained there, 62 mmol of 4,4′-diiodobiphenyl, 1.3 mmol of palladium acetate, 5.2 mmol of t-butylphosphine, 260 mmol of t-butoxynatrim and 700 mL of xylene were mixed and stirred at 120 ° C. did. Thereafter, the mixture was allowed to cool and crystallized to obtain a compound.

And mass spectrum (MS) method, ¹ H-nuclear magnetic resonance ( ¹ H-NMR) spectrum method, ¹³ C-nuclear magnetic resonance ( ¹³ C-NMR) spectrum method, and Fourier transform infrared absorption (FT-IR) It was confirmed by a spectral method that the obtained compound was the following compound (A).

2. Production of display device (Example 1)
<1A> First, a polyimide substrate having an average thickness of 0.5 mm and a transparent glass substrate having an average thickness of 5 mm were prepared. And the circuit part was formed on this glass substrate as mentioned above.

  <2A> Next, an ITO film having an average thickness of 150 nm was formed on the polyimide substrate by vacuum deposition to obtain an anode.

  <3A> Next, after applying polyimide (insulating photosensitive resin) so as to cover the anode, along the outer periphery of the region where the hole transport layer is formed, a part of the height is low. In this way, the first protrusion as shown in FIG. 2 was formed by exposing the applied polyimide.

  At this time, an alignment mark was formed.

  <4A> Next, after applying polyimide (insulating photosensitive resin) so as to cover the circuit portion provided on the glass substrate, it was applied along the outer peripheral portion of the region where the hole transport layer was formed. By exposing the polyimide, second protrusions as shown in FIG. 2 were formed.

  <5A> Next, a Cu layer having an average thickness of 50 nm was formed on the circuit portion inside the second protrusion by an electroless plating method to obtain a cathode.

<6A> Next, an xylene solution of a polymer complex of 8-hydroxyquinoline aluminum (Alq ₃ ) was supplied onto the cathode inside the second protrusion by an ink jet method, and then dried to obtain an average thickness of 50 nm. An electron transport layer was formed.

  <7A> Next, poly (9,9-dioctyl-2,7-divinylenefluorenyl-ortho-co (anthracene-9,10) is formed on the electron transport layer inside the second protrusion by an inkjet method. -Diyl) (weight average molecular weight 200000) xylene solution was supplied and then dried to form a light emitting layer having an average thickness of 50 nm.

  At this time, an alignment mark was formed.

  <8A> Next, as shown in FIG. 3D, the first protrusion and the second protrusion were brought into contact with each other to form a protrusion. Thereby, a gap for injecting the hole transport material and a second liquid injection part were formed.

  <9A> Next, the gap was sealed with an epoxy adhesive at the edge of the glass substrate and the polyimide substrate, and the substrates were bonded together.

  <10A> Next, as shown in FIG. 4B, that is, a hole was provided in the polyimide substrate in the thickness direction by a plasma etching method so as not to overlap with the region where the light emitting layer was formed.

  <11A> Next, the bonded body of the glass substrate and the polyimide substrate obtained through the steps <1A> to <10A> was placed in a chamber, and then the pressure was reduced.

Note that the pressure in the chamber at this time was 10 ² Pa.

  <12A> Next, the compound (A) was supplied by an ink jet method so as to close the holes provided in the polyimide substrate.

  <13A> Next, the compound (A) supplied so as to close the hole on the polyimide substrate is injected into the gap as shown in FIG. 5B by returning the pressure in the chamber to atmospheric pressure. As a result, a hole transport layer having an average thickness of 30 nm was formed.

  <14A> Next, the hole provided in the polyimide substrate was sealed with an epoxy adhesive to form a display device.

(Example 2)
<1B> First, a first glass substrate having an average thickness of 0.5 mm and a transparent second glass substrate having an average thickness of 0.5 mm were prepared.

  And after applying polyimide (insulating photosensitive resin) on the 1st glass substrate, the polyimide layer with an average thickness of 10 micrometers was formed by exposing.

  Further, a circuit portion was formed on the second glass substrate as described above.

  <2B> Next, an ITO film having an average thickness of 150 nm was formed by vacuum deposition on the surface of the first glass substrate on which the polyimide layer was not formed (the surface opposite to the surface) to obtain an anode.

  <3B> Next, after applying polyimide (insulating photosensitive resin) so as to cover the anode, along the outer periphery of the region where the hole transport layer is formed, a part of the height is low. Thus, the applied polyimide was exposed to form first protrusions as shown in FIG.

  At this time, an alignment mark was formed.

  <4B> Next, as shown in FIG. 9B, a liquid repellent treatment was performed on the surface of the first glass substrate on the polyimide layer side.

  Various conditions for the liquid repellent treatment (fluorine plasma treatment) are as follows.

・ Fluorine-containing gas: Tetrafluoromethane gas ・ Gas flow rate: 350 sccm
RF power: 0.05 W / cm ²
Fluorine plasma irradiation time: 30 seconds <5B> Next, as shown in FIG. 9D, that is, a polyimide layer was formed by a plasma etching method so as not to overlap with the region where the light emitting layer was formed. A hole provided with a first hole and a second hole having a smaller cross section than the first hole in the thickness direction of the first glass substrate was provided.

  <6B> Next, after applying polyimide (insulating photosensitive resin) so as to cover the circuit portion provided on the second glass substrate, along the outer peripheral portion of the region where the hole transport layer is formed. By exposing the applied polyimide, second protrusions as shown in FIG. 7 were formed.

  <7B> Next, a Cu layer having an average thickness of 50 nm was formed on the circuit portion inside the second protrusion by an electroless plating method to obtain a cathode.

<8B> Next, an xylene solution of a polymer complex of 8-hydroxyquinoline aluminum (Alq ₃ ) is supplied onto the cathode inside the second protrusion by an ink jet method, and then dried to have an average thickness of 50 nm. An electron transport layer was formed.

  <9B> Next, poly (9,9-dioctyl-2,7-divinylenefluorenyl-ortho-co (anthracene-9,10) is formed on the electron transport layer inside the second protrusion by an inkjet method. -Diyl) (weight average molecular weight 200000) xylene solution was supplied and then dried to form a light emitting layer having an average thickness of 50 nm.

  At this time, an alignment mark was formed.

  <10B> Next, as shown in FIG. 10C, the first protrusion and the second protrusion were brought into contact with each other to form a protrusion. Thereby, a gap for injecting the liquid material and a liquid injection part were formed.

  <11B> Next, the gap was sealed with an epoxy-based adhesive at the edges of the first glass substrate and the second substrate, and the substrates were bonded to each other.

  <12B> Next, the bonded body of the first glass substrate and the second glass substrate obtained through the steps <1B> to <11B> was placed in the chamber, and then the pressure was reduced.

Note that the pressure in the chamber at this time was 10 ² Pa.

  <13B> Next, the compound (A) was supplied by an inkjet method so as to close the hole provided on the first glass substrate side.

  <14B> Next, by returning the pressure in the chamber to atmospheric pressure, the compound (A) supplied so as to close the hole on the first glass substrate side is replaced with a gap as shown in FIG. To form a hole transport layer having an average thickness of 30 nm.

  <15B> Next, a hole provided on the first glass substrate side was sealed with an epoxy adhesive to form a display device.

For the display devices of Examples 1 and 2, the current density (mA / cm ² ), light emission luminance (cd / m ² ), and maximum light emission efficiency (lm / W) were measured, and the light emission luminance was an initial value. The half-life time (half-life) was measured and all showed excellent results.

  Note that the current density and the luminance were measured by applying a voltage of 6 V between the anode and the cathode.

  According to the present invention, an organic light emitting device is provided with a first substrate and a second substrate, and a layer other than the carrier transport layer is applied on the inner surface side of the first substrate and / or the second substrate. After forming by the phase film forming method or the vapor phase film forming method, the first substrate and the second substrate are joined so that a gap is formed between them, and then from the first liquid injection portion The carrier transport material is manufactured by injecting the carrier transport material into the gap. By manufacturing an organic light-emitting device using such a method for manufacturing an organic light-emitting device, the carrier transport layer is formed not only when it is configured with a solid carrier transport material but also with a liquid or semi-solid carrier transport material. Therefore, there is an advantage that the range of selection of the carrier transport material used for the carrier transport layer is widened. In addition, an electronic device including the organic light emitting device manufactured by the method for manufacturing the organic light emitting device is highly reliable. Therefore, it has industrial applicability.

Claims (33)

Of the cathode, anode, light emitting layer and at least one carrier transport layer constituting the organic light emitting device sandwiched between the first substrate and the second substrate, other than the carrier transport layer composed of a predetermined carrier transport material A layer is formed by a liquid phase film formation method or a gas phase film formation method, and the carrier transport layer composed of the predetermined carrier transport material is formed by another method, thereby forming the organic light emitting element having a laminated structure. A method of manufacturing an organic light emitting device,
After forming a layer other than the carrier transport layer on the inner surface side of the first substrate and / or the second substrate by a liquid phase film formation method or a gas phase film formation method,
Bonding the first substrate and the second substrate such that a gap is formed between them;
Next, a method of manufacturing an organic light emitting device, wherein the carrier transport layer is formed by injecting the predetermined carrier transport material into the gap from a first liquid injection section. 2. The method of manufacturing an organic light emitting device according to claim 1, wherein the first liquid injection part is a hole formed in the first substrate or the second substrate. 3. The method of manufacturing an organic light emitting device according to claim 2, wherein the hole is provided so as not to overlap with a region where the light emitting layer is formed. The method for manufacturing an organic light-emitting device according to claim 2, wherein the hole has a liquid repellent treatment around the hole. The organic light-emitting device according to claim 2, wherein the hole is formed after a liquid repellent treatment is performed on a region including the region where the hole is formed on the first substrate or the second substrate. Method. The method for manufacturing an organic light-emitting device according to claim 2, wherein a lyophilic treatment is applied to the inside of the hole. The range according to claim 2, wherein the hole is constituted by a first hole and a second hole that communicates with the first hole on the gap side and that is smaller than a cross section of the first hole. The manufacturing method of the organic light-emitting device of description. The method for manufacturing an organic light-emitting device according to claim 7, wherein the predetermined carrier transport material is supplied so as to fill the first hole. The contact angle of the predetermined carrier transport material in the region where the liquid repellent treatment is performed on the first substrate or the second substrate is A [°], and the predetermined carrier transport material in the first hole is The manufacturing method of the organic light-emitting device according to claim 8, wherein a relationship of AB ≧ 15 ° is satisfied, where B is a contact angle of B [°]. The method for manufacturing an organic light-emitting device according to claim 2, wherein a layer other than the carrier transport layer is formed after forming the holes. The method for manufacturing an organic light-emitting device according to claim 2, wherein the hole is formed after the layers other than the carrier transport layer are formed and before the first substrate and the second substrate are bonded. 3. The method of manufacturing an organic light emitting device according to claim 2, wherein the hole is formed after the first substrate and the second substrate are joined. The method of manufacturing an organic light emitting device according to claim 1, wherein the thickness of the gap is controlled by a spacer. The spacer is composed of protrusions formed along the outer periphery of the region forming the carrier transport layer,
14. The organic light emitting device according to claim 13, wherein the protrusion is provided with a second liquid injection portion for injecting the predetermined carrier transport material injected from the first liquid injection portion into the gap. Device manufacturing method. The protrusion is formed by bringing a first protrusion provided on the first substrate side into contact with a second protrusion provided on the second substrate side,
The second liquid injecting section lowers the height of a part of the first protrusion and / or the height of a part of the second protrusion, and the first protrusion and the second protrusion The method for producing an organic light-emitting device according to claim 14, wherein the organic light-emitting device is obtained by contacting the substrate. The protrusion is formed by bringing a first protrusion provided on the first substrate side into contact with a second protrusion provided on the second substrate side,
The method of manufacturing an organic light-emitting device according to claim 14, wherein the second liquid injection part is a through hole provided in one of the first protrusion and the second protrusion. The method of manufacturing an organic light emitting device according to claim 13, wherein the spacer is made of particles. The method of manufacturing an organic light-emitting device according to claim 17, wherein the particles are disposed in the gap. The method for manufacturing an organic light-emitting device according to claim 1, wherein the predetermined carrier transport material is supplied to the first liquid injection portion using an inkjet method. After reducing the atmosphere of the gap and supplying the predetermined carrier transport material so as to close the first liquid injection portion, the difference between the pressure of the gap and the atmospheric pressure is used to The method for manufacturing an organic light-emitting device according to claim 1, wherein a carrier transport material is injected into the gap. 21. The method of manufacturing an organic light-emitting device according to claim 20, wherein a pressure difference between the atmospheric pressure and the gap is about 1.0 × 10 ^{−4 to} 1.0 × 10 ¹² Pa. Prior to injecting the predetermined carrier transport material supplied to close the first liquid injection portion into the gap,
21. The method of manufacturing an organic light-emitting device according to claim 20, wherein the predetermined carrier transport material is heated to reduce the viscosity of the carrier transport material. 23. The method of manufacturing an organic light-emitting device according to claim 22, wherein the predetermined carrier transporting material is heated by heating one or both of the first substrate and the second substrate. 2. The method for manufacturing an organic light emitting device according to claim 1, wherein the predetermined carrier transport material is a hole transport material. The predetermined carrier transport material is mainly composed of a hole transport material composed of a hole transport part having a function of transporting holes and at least one linear alkyl group linked to the hole transport part. 25. A method of manufacturing an organic light emitting device according to claim 24. Liquid phase film forming method of layers other than the hole transport layer among the cathode, anode, light emitting layer, hole transport layer and electron transport layer constituting the organic light emitting device sandwiched between the first substrate and the second substrate Alternatively, it is a method for manufacturing an organic light-emitting device, in which the organic light-emitting element having a multilayer structure is manufactured by forming the hole-transporting layer composed of a hole-transporting material by another method. And
Forming the anode on the first substrate;
Forming a first protrusion on the anode along the outer periphery of the region where the hole transport layer is to be formed and so that a part of the height thereof is lowered;
Forming a second protrusion on the second substrate along an outer periphery of a region where the hole transport layer is formed;
Forming the cathode, the electron transport layer, and the light emitting layer in this order on the second substrate exposed inside the second protrusion;
A gap between the first substrate and the second substrate, and a second liquid injection part for injecting the hole transport material into the gap between the first protrusion and the second protrusion Contacting the first protrusion and the second protrusion so that each is formed,
Bonding the first substrate and the second substrate by forming a sealing portion that seals the gap at their edges; and
Forming a first liquid injection portion by providing a hole in the thickness direction in the first substrate so as not to overlap a region where the light emitting layer is formed;
Depressurizing the gap;
Supplying the hole transport material so as to block the first liquid injection part;
Utilizing the difference in pressure between the gap and atmospheric pressure to form the hole transport layer by injecting the hole transport material into the gap;
And a step of sealing the first liquid injection part. Among the cathode, the anode, the light emitting layer, the hole transport layer, and the electron transport layer constituting the organic light emitting device sandwiched between the first substrate and the second substrate, a layer other than the electron transport layer is formed by a liquid phase film formation method or A method for producing an organic light-emitting device, wherein the organic light-emitting device having a multilayer structure is produced by forming the electron-transporting layer formed of a vapor-phase film-forming method and the electron-transporting material by another method,
Forming the anode on the first substrate;
Forming a first protrusion on the anode along the outer peripheral portion of the region where the electron transport layer is formed and so that a part of the height thereof is lowered;
Forming a second protrusion on the second substrate along an outer periphery of a region where the electron transport layer is formed;
On the anode exposed inside the first protrusion, the hole transport layer and the light emitting layer are formed in this order, and on the second substrate exposed inside the second protrusion, Forming the cathode;
There is a gap between the first substrate and the second substrate, and a second liquid injection section for injecting the electron transport material into the gap between the first protrusion and the second protrusion. Bringing the first protrusion and the second protrusion into contact with each other so as to be formed respectively;
Bonding the first substrate and the second substrate by forming a sealing portion that seals the gap at their edges; and
Forming a first liquid injection portion by providing a hole in the thickness direction in the first substrate so as not to overlap a region where the light emitting layer is formed;
Depressurizing the gap;
Supplying the electron transport material so as to block the first liquid injection part;
Using the difference in pressure between the gap and atmospheric pressure to form the electron transport layer by injecting the electron transport material into the gap;
And a step of sealing the first liquid injection part. Liquid phase film forming method of layers other than the hole transport layer among the cathode, anode, light emitting layer, hole transport layer and electron transport layer constituting the organic light emitting device sandwiched between the first substrate and the second substrate Alternatively, it is a method for manufacturing an organic light-emitting device, in which the organic light-emitting element having a multilayer structure is manufactured by forming the hole-transporting layer composed of a hole-transporting material by another method. And
Forming the anode on the first substrate;
Forming a first protrusion on the anode along the outer periphery of the region where the hole transport layer is to be formed and so that a part of the height thereof is lowered;
Applying a liquid repellent treatment to the surface of the first substrate opposite to the anode;
A step of forming a first liquid injection part by providing a hole in the thickness direction in the first substrate that has been subjected to the liquid repellent treatment so as not to overlap with a region where the light emitting layer is to be formed. When,
Forming a second protrusion on the second substrate along an outer periphery of a region where the hole transport layer is formed;
Forming the cathode, the electron transport layer, and the light emitting layer in this order on the second substrate exposed inside the second protrusion;
A gap between the first substrate and the second substrate, and a second liquid injection part for injecting the hole transport material into the gap between the first protrusion and the second protrusion Contacting the first protrusion and the second protrusion so that each is formed,
Bonding the first substrate and the second substrate by forming a sealing portion that seals the gap at their edges; and
Depressurizing the gap;
Supplying the hole transport material so as to block the first liquid injection part;
Utilizing the difference in pressure between the gap and atmospheric pressure to form the hole transport layer by injecting the hole transport material into the gap;
And a step of sealing the first liquid injection part. Among the cathode, the anode, the light emitting layer, the hole transport layer, and the electron transport layer constituting the organic light emitting device sandwiched between the first substrate and the second substrate, a layer other than the electron transport layer is formed by a liquid phase film formation method or A method for producing an organic light-emitting device, wherein the organic light-emitting device having a multilayer structure is produced by forming the electron-transporting layer formed of a vapor-phase film-forming method and the electron-transporting material by another method,
Forming the anode on the first substrate;
Forming a first protrusion on the anode along the outer peripheral portion of the region where the electron transport layer is formed and so that a part of the height thereof is lowered;
Applying a liquid repellent treatment to the surface of the first substrate opposite to the anode;
A step of forming a first liquid injection part by providing a hole in the thickness direction in the first substrate that has been subjected to the liquid repellent treatment so as not to overlap with a region where the light emitting layer is to be formed. When,
Forming a second protrusion on the second substrate along an outer periphery of a region where the electron transport layer is formed;
On the anode exposed inside the first protrusion, the hole transport layer and the light emitting layer are formed in this order, and on the second substrate exposed inside the second protrusion, Forming the cathode;
There is a gap between the first substrate and the second substrate, and a second liquid injection section for injecting the electron transport material into the gap between the first protrusion and the second protrusion. Bringing the first protrusion and the second protrusion into contact with each other so as to be formed respectively;
Bonding the first substrate and the second substrate by forming a sealing portion that seals the gap at their edges; and
Depressurizing the gap;
Supplying the electron transport material so as to block the first liquid injection part;
Using the difference in pressure between the gap and atmospheric pressure to form the electron transport layer by injecting the electron transport material into the gap;
And a step of sealing the first liquid injection part. The manufacturing method of the organic light-emitting device according to claim 1, comprising a plurality of the organic light-emitting elements. 31. The method for manufacturing an organic light emitting device according to claim 30, wherein a carrier transport layer constituting the organic light emitting element is formed integrally with the plurality of organic light emitting elements. An organic light-emitting device manufactured by the method for manufacturing an organic light-emitting device according to claim 1. An electronic apparatus comprising the organic light-emitting device according to claim 32.

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