JP2008047890A - Organic device and organic device manufacturing method - Google Patents

Abstract

An organic device that uses a hole injection material that is easy to inject holes into an organic layer and has adhesion stability with the organic layer and that has a long driving life and an easy manufacturing process, and the organic device A manufacturing method is provided.
A compound contained in an organic layer has, as part of its chemical structure, a portion A having a total atomic weight MA of 100 or more, and a hole injecting material contained in the hole injecting layer has its chemistry. As a part of the structure, the linking group that produces an effect of linking to the electrode on which the hole injection material is laminated, and the total amount MB of the atomic weight are 100 or more, and the total amount MB of the atomic weight and the portion A of the organic layer The sum MA of atomic weights of the atoms included satisfies a specific relationship, and the sum MA of the atomic weights has a portion A that is greater than 1/3 of the molecular weight of the hole injection material, the solubility parameter SA of the portion A, and An organic device characterized in that the solubility parameter SB of the portion B satisfies a specific relationship.
[Selection] Figure 1

Description

  The present invention relates to an organic device and a method for manufacturing the organic device.

  Organic devices are expected to be developed into a wide range of basic elements and applications, such as organic electroluminescence elements (hereinafter referred to as organic EL elements), organic transistors, and organic solar cells.

  An organic EL element is a charge injection type self-luminous device that utilizes light emission generated when electrons and holes that have reached a light emitting layer recombine. This organic EL element was developed in 1987 by T.W. W. Since Tang et al. Demonstrated that a device in which a thin film composed of a fluorescent metal chelate complex and a diamine-based molecule is laminated exhibits high-luminance light emission at a low driving voltage, it has been actively developed.

The element structure of the organic EL element is composed of cathode / organic layer / anode. This organic layer had a two-layer structure consisting of a light emitting layer / hole injection layer in the early organic EL elements, but now, in order to obtain high luminous efficiency and a long driving life, an electron injection layer / electron layer is used. Various multilayer structures such as a five-layer structure composed of a transport layer / a light emitting layer / a hole transport layer / a hole injection layer have been proposed.
The electron injection layer, electron transport layer, hole transport layer, hole injection layer, and other layers other than the light-emitting layer can maintain the balance between electron current and hole current by facilitating injection or blocking. It is said that there are effects such as suppressing the diffusion of light energy excitons.

Among these organic layers, the hole injection layer in contact with the anode is not only intended to facilitate injection of holes from the anode to the hole transport layer or from the anode to the light emitting layer, but also for the purpose of smoothing the anode surface. Also used. Therefore, the material used for the hole injection layer has a HOMO energy that reduces the hole injection energy barrier from the anode to the hole transport layer or from the anode to the light emitting layer, thereby improving the film forming property and the stability of the thin film. It is desirable to have excellent characteristics. Here, HOMO energy and film-forming property are related to high-efficiency driving of the initial characteristics of the device, and film-forming property and thin-film stability are related to the lifetime property and driving stability of the device.
The term “lifetime” as used herein means the luminance half-life time when the organic EL element is continuously driven by constant current drive or the like, and the longer the half-life time is, the longer the drive life is. The driving stability here is a state in which there is no short-circuit between electrodes caused by conductive protrusions on the substrate or pinholes formed by dust, and is distinguished from life characteristics.

  As a study for providing a hole injection layer in contact with the anode, for example, ITO (a transparent electrode made of an oxide of indium and tin) as an anode, CuPc (copper phthalocyanine) as an anode buffer layer, and TPD (triphenyl) as a hole transport layer Diamine derivatives), Alq3 (aluminum complex) as an electron transport layer that also serves as a light emitting layer, LiF (lithium fluoride) as a cathode buffer layer, and Al (aluminum) as a cathode, and an organic EL element configured in this order (For example, refer nonpatent literature 1). However, CuPc used for the anode buffer layer has a surface shape that directly reflects the unevenness of the underlying ITO substrate because it is deposited by vacuum deposition, and it cannot be thickened because it has absorption in the visible light region. There was a problem in driving stability due to short circuit between electrodes.

  In order to remedy such drawbacks, attempts have been made to provide a hole injection layer by a coating method. Patent Document 1 proposes an organic EL element that employs poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT-PSS) as an anode buffer layer. The anode buffer layer of PEDOT-PSS can be formed on the surface of the anode using a spin coating method. When the hole injection layer is formed by the coating method in this way, even if the substrate such as ITO has irregularities, an anode buffer layer with a flat surface can be formed while filling the irregularities, and even if the film thickness is thin, the electrode It is possible to reduce the problem of short circuit and to produce an element with excellent driving stability. However, further improvement in adhesion stability with the hole transport layer is required from the viewpoint of extending the life.

  Patent Document 2 reports an organic EL element in which an organic thin film having a dipole moment and having an electric double layer effect on the surface of the anode on the light emitting layer side is formed as a hole injection layer. In this report, the action of the organic thin film having the dipole moment reduces the energy gap between the electrode and the organic layer, facilitates hole injection from the anode to the light emitting layer, and achieves a low driving voltage. It is described. Patent Document 3 discloses an organic EL element in which a light emitting layer containing a liquid crystalline organic material is provided between a substrate on which a first electrode is formed and a substrate on which a second electrode is formed. An organic EL element in which an organic thin film having a dipole moment is formed between one or both of the first electrode and the second electrode and the light emitting layer has been reported. This report describes that the organic thin film acts as an electric double layer that reduces the energy gap between the electrode and the organic layer, facilitating injection of charges from the electrode to the light emitting layer. However, these organic EL elements are inventions aimed at improving charge injection in the initial characteristics, and sufficient studies have not been made on extending their lifetime.

  On the other hand, an organic transistor is a thin film transistor that uses an organic semiconductor material composed of a π-conjugated organic polymer or a small organic molecule in a channel region. A general organic transistor includes a substrate, a gate electrode, a gate insulating layer, source / drain electrodes, and an organic semiconductor layer. In an organic transistor, by changing the voltage (gate voltage) applied to the gate electrode, the amount of charge at the interface between the gate insulating film and the organic semiconductor film is controlled, and the current value between the source electrode and the drain electrode is changed. Perform switching.

  Introducing a charge transfer complex into an organic semiconductor as an attempt to improve the on-current value of the organic transistor and stabilize the device characteristics by reducing the charge injection barrier between the organic semiconductor layer and the source or drain electrode This is known to increase the carrier density in the organic semiconductor layer in the vicinity of the electrode (for example, Patent Document 4). However, the device structure in which the charge transfer complex is introduced into the entire semiconductor layer as in Patent Document 4 has a problem that the off-current also increases and the current on / off ratio is deteriorated. From this point of view, further improvement was necessary. As in Patent Document 5, there is an attempt to form a self-assembled film of a silane compound on a gate insulating film for the purpose of high performance and high reliability of a transistor, but adhesion between a source or drain electrode and an organic semiconductor material is known. Stability was not considered. In addition, as in Patent Document 2, when an organic thin film having a large dipole moment is formed on an electrode as a hole injection layer, hysteresis is caused in current-voltage characteristics due to reversal of molecules when driving voltage is turned on and off. There is a problem in application to organic transistors.

JP 2004-228002 A JP 2002-270369 A JP 2005-50553 A JP-A-5-55568 JP-A-2005-39222 E. W. Forsythe, M .; A. Abkouitz, Y .; Gao, and C.C. W. Tang, “Influence of copper phthalocyanine on the charge injection and growth modes for organic light emitting diodes,” J. Vac. Sci. Technol. A, vol. 18, no. 4, pp. 1869-1874, 2001. “Basic Theory of Adhesion”, Satoshi Imoto, Polymer Publishing Society, p71-134 “What does adhesion mean?” Imoto Satoshi, Huang Keiun, Iwanami Shinsho, p33-54

The inventors focused on the adhesion stability of the anode / organic layer (hole transport layer or light-emitting layer) interface as one countermeasure for suppressing the luminance deterioration of the organic EL element.
In many cases, an inorganic material such as a metal or a metal oxide is used for the anode of the organic EL element, but these have a very large surface tension as compared with the organic material. That is, the cohesive force is very large, and the solubility parameter (SP value) is also very large (Non-patent Documents 2 and 3). Even if an organic layer is formed on this high energy surface by any method, the wettability of the inorganic / organic interface having a difference in SP value is low and is an unstable metastable state.

FIG. 4 is a conceptual cross-sectional view of a laminate in which an organic layer is laminated on an electrode made of an inorganic material and there is a difference in SP value between both materials forming an interface. At the beginning of lamination, even if it is a laminate without voids as shown in FIG. 4A, when organic molecules can move, for example, when the temperature is higher than the glass transition temperature (Tg) of the organic molecules, or below Tg However, when the device is driven, the organic molecules in the vicinity of the interface are in an energetically stable state as shown in FIG. 4B, that is, the molecules are reduced so that the contact area of the inorganic / organic interface is as small as possible. Moving.
On the other hand, even if the organic molecules can move, if there is no difference in the SP values of the two materials forming the interface, the wet and spread state is an energetically stable state. The contact area of the organic interface is not easily changed and is stable.

It should be noted here that the driven molecule can move even at temperatures below Tg. The electronic structure of the molecule of the hole injecting / transporting material repeats a ground state and a cation state each time a hole is transported to an adjacent molecule. Since the shape of the molecule is generally different between the ground state and the cation state, the molecule moves violently within the molecule while transporting holes. In a thin film where molecules are close to each other, intramolecular motion is converted into relative motion between molecules, that is, molecules can move by driving even below Tg.
When a gap of 1 nm or more is generated between the electrode layer and the organic layer at the inorganic / organic interface whose contact area is reduced by continuous driving, intermolecular charge transfer is possible with an intermolecular distance of about 1 to 2 nm or less. Since this is a phenomenon, it is considered that the hole injection characteristic deteriorates at the anode / organic layer interface where the gap is generated, the drive voltage becomes higher, the carrier balance changes from the initial state, and the luminance deteriorates.

  As described above, when a compound having an SP value between an anode having a large SP value and an organic layer having a small SP value is used for the hole injection layer, a gap on the order of nm is obtained when the organic EL element is driven. It is predicted that no molecular movement will occur and the contact area in the initial state before driving can be maintained even during driving.

  From this point of view, looking at the materials used for the hole injection layer in the existing technology, the compound used in Patent Document 3 has a dipole moment as a whole molecule, not only a part of the molecule. In many cases, it has a high polarity, and when a material with a small polarity is laminated on the organic layer, the compatibility is low and the adhesion stability may be poor.

  On the other hand, CuPc used in Non-Patent Document 1 is a metal-containing organic compound, and since the SP value of the central metal is high, PEDOT: PSS used in Patent Document 1 has a relatively SP value. Since the large sulfonic acid group is contained, the SP value of the whole molecule is large (the polarity of the whole molecule is large), and these are considered to have relatively high adhesion stability with the surface of an inorganic substance such as ITO.

However, when viewed on a length scale of the nm order, for example, PEDOT-PSS is a mixed polymer of a PEDOT site having a small polarity and a PSS site having a high polarity. In particular, a gap is generated at the PSS site, and there is a concern about the stability of adhesion with the organic layer during driving. Similarly, in CuPc, there is a concern about adhesion stability with the organic layer.
Therefore, it is necessary to design a layer structure in consideration of the average SP value (molecular polarity) of the whole molecule of the compound contained in each of the hole injection layer and the organic layer. In consideration of local SP value (molecular polarity) matching in each layer, and local SP value (molecular polarity) matching in the nm-scale molecules of the hole injection material and the material contained in the organic layer, The design of the layer structure for selecting the material is considered important.
In addition, such a layer configuration design is considered to be applicable not only to organic EL elements but also to various elements that require injection of holes from an electrode to an organic layer.

  Based on the above considerations, the present invention is an organic material that can easily inject holes into the organic layer, has a long driving life, and has an easy manufacturing process using a hole injecting material having adhesion stability with the organic layer. It is an object to provide a device and a method for manufacturing the organic device.

As a result of diligent studies to achieve the above object, the present inventors have focused on the adhesion stability of the anode / organic layer interface as one measure for suppressing luminance deterioration, and have a solubility close to that of the hole transport layer material. By using a material having a parameter (SP value) and a linking group of an electrode having an SP value close to that of the anode in the molecule for the hole injection layer, the inventors have obtained the knowledge that the above problems can be solved. It came to complete.
That is, the organic device of the present invention includes two or more electrodes facing on a substrate, an organic layer disposed between the two electrodes, and hole injection adjacent to the organic layer side surface of at least one electrode. An organic device that may further include a metal layer on the electrode,
The compound contained in the organic layer has, as part of its chemical structure, a portion A having a total atomic mass MA of 100 or more,
The hole injection material contained in the hole injection layer has, as part of its chemical structure, a linking group that has an effect of linking with the electrode on which the hole injection material is laminated, and the total atomic weight MB is 100 or more. The sum MB of the atomic weights and the sum MA of the atomic weights of the atoms contained in the portion A of the organic layer satisfy the relationship of the following formula (I), and the sum MB of the atomic weights is 1 / of the molecular weight of the hole injection material. Having a portion B greater than 3;
The solubility parameter SA of the part A and the solubility parameter SB of the part B satisfy the relationship of the following formula (II).
| MA-MB | / MB ≦ 2 Formula (I)
| SA-SB | ≦ 2 Formula (II)

  When the relationship between the SP value of the part B of the compound contained in the organic layer and the part A of the hole injection material satisfies the relational expression (I), the molecular polarity matching between the part A and the part B is good. Therefore, the adhesion at the interface between the hole injection layer and the hole transport layer can be kept stable, which contributes to a longer driving life of the organic device. In addition, since the hole injection material has a linking group connected to an electrode on which the hole injection material is stacked (hereinafter sometimes referred to as a hole injection electrode), the hole injection layer and the electrode It is possible to keep the adhesion of the interface with the stable and contribute to the long driving life of the organic device.

The hole injection layer preferably contains a hole injection material represented by the following general formula (1).
XY (1)
However, X includes the portion B. Y is a connecting group connected to the electrode.

  The portion B has the same skeleton as the portion A or a similar skeleton including a spacer structure in the same skeleton, which improves the adhesion stability at the interface between the hole injection layer and the organic layer, and has a long driving life. It is preferable from the point of contributing to the conversion.

  When the hole injection material is a compound represented by the general formula (1), the sum MB of the atomic weights of the atoms contained in the portion B is larger than 1/3 of the sum of the atomic weights of the atoms contained in X. However, it is preferable from the viewpoint of further improving the adhesion stability of the interface between the hole injection layer and the organic layer and contributing to a longer driving life.

  The thickness of the hole injection layer is preferably 0.1 to 100 nm from the viewpoint of hole injection efficiency.

  The work function of the hole injection layer is preferably 5 to 6.0 eV from the viewpoint of hole injection efficiency.

  The hole injection layer is preferably formed by a solution coating method because a vapor deposition apparatus is unnecessary, productivity is high, and interface adhesion stability is high. Similarly, the hole transport layer is preferably formed on the hole injection layer by a solution coating method.

The organic EL element which is one embodiment of the organic device of the present invention is characterized in that the organic device has at least a hole transport layer and a light emitting layer as an organic layer.
The hole transport material contained in the hole transport layer is a compound represented by the following general formula (2), and the hole injection material is a compound represented by the following general formula (3). This is preferable from the viewpoint of improving the adhesion stability of the interface between the layer and the hole transport layer and contributing to a longer driving life.

(However, Ar _{1 to} Ar ₄ may be the same as or different from each other, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 60 carbon atoms related to the conjugated bond, or An unsubstituted or substituted heterocyclic group having 4 or more and 60 or less carbon atoms related to a conjugated bond is shown, n is 0 to 10,000, m is 0 to 10,000, and n + m = 1 to 20,000. The arrangement of the two repeating units is arbitrary.)

(However, Ar _{5 to} Ar ₇ may be the same as or different from each other, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 60 carbon atoms related to the conjugated bond, or An unsubstituted or substituted heterocyclic group having 4 to 60 carbon atoms with respect to a conjugated bond is shown.)

The organic device manufacturing method of the present invention includes two or more electrodes opposed on a substrate, an organic layer disposed between the two electrodes, and holes adjacent to the organic layer side surface of at least one electrode. And a method for producing an organic device that may further include a metal layer on the electrode,
The compound contained in the organic layer has a part A having a total atomic weight MA of 100 or more as a part of the chemical structure, and the hole injection material contained in the hole injection layer is connected to the electrode. The total MB of the atomic weights and the atomic weight total MB and the total atomic mass MA of the atoms contained in the portion A of the organic layer satisfy the relationship of the following formula (I), In the organic device having the portion B in which the total atomic weight MB is larger than 1/3 of the molecular weight of the hole injection material, the solubility parameter SA of the portion A and the solubility parameter SB of the portion B are expressed by the following formula (II). Meet relationships,
| MA-MB | / MB ≦ 2 Formula (I)
| SA-SB | ≦ 2 Formula (II)
The manufacturing method includes a step of preparing a substrate provided with an electrode;
Applying a solution containing at least the hole injection material having the portion B to form a hole injection layer;
It is characterized by having a step of forming an organic layer by applying a solution containing at least the compound having the portion A on the hole injection layer.
By using the above-mentioned materials by solution coating, an organic vapor deposition apparatus is unnecessary, the productivity is high, and the adhesion stability between the electrode and the hole injection layer and the interface between the hole injection layer and the organic layer is high. This is preferable because a device can be formed.

In the method for producing an organic device of the present invention, the hole injection layer preferably contains a hole injection material represented by the following general formula (1).
XY (1)
However, X includes the portion B. Y is a connecting group connected to the electrode.

  In the method for producing an organic device of the present invention, it is preferable that the part B has the same skeleton as the part A or a similar skeleton including a spacer structure in the same skeleton.

  In the method for producing an organic device of the present invention, when the hole injection material is a compound represented by the general formula (1), the atomic weight of atoms in which the total MB of the atomic weights of the atoms contained in the portion B is contained in X It is preferable that it is larger than 1/3 of the sum total.

  An organic EL device manufacturing method according to an embodiment of an organic device manufacturing method according to the present invention includes a step of forming the organic layer, wherein the organic layer includes a hole transport layer and a light emitting layer, and the hole injection layer. And a step of forming a hole transport layer and a light-emitting layer in this order on the surface.

  In the method for producing an organic EL element, the hole transport material contained in the hole transport layer is a compound represented by the following general formula (2), and the hole injection material is represented by the following general formula (3). A compound is preferred.

(However, Ar _{1 to} Ar ₄ may be the same as or different from each other, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 60 carbon atoms related to the conjugated bond, or An unsubstituted or substituted heterocyclic group having 4 or more and 60 or less carbon atoms related to a conjugated bond is shown, n is 0 to 10,000, m is 0 to 10,000, and n + m = 1 to 20,000. The arrangement of the two repeating units is arbitrary.)

(However, Ar _{5 to} Ar ₇ may be the same as or different from each other, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 60 carbon atoms related to the conjugated bond, or An unsubstituted or substituted heterocyclic group having 4 to 60 carbon atoms with respect to a conjugated bond is shown.)

  According to the present invention, two or more electrodes facing on a substrate, an organic layer disposed between the two electrodes, a hole injection layer adjacent to the organic layer side surface of at least one electrode, In addition, an organic device that may have a metal layer on the electrode, the hole injection material that is easy to inject holes into the organic layer and has adhesion stability of the organic layer By using this, it is possible to provide an organic device having a long driving life and an easy manufacturing process, and a method for manufacturing the organic device.

1. Organic device The organic device of the present invention comprises two or more electrodes facing each other on a substrate, an organic layer disposed between the two electrodes, and holes adjacent to the organic layer side surface of at least one electrode. And an injection layer, and further an organic device that may have a metal layer on the electrode,
The compound contained in the organic layer has, as part of its chemical structure, a portion A having a total atomic mass MA of 100 or more,
The hole injection material contained in the hole injection layer has, as part of its chemical structure, a linking group that has an effect of linking with the electrode on which the hole injection material is laminated, and the total atomic weight MB is 100 or more. The sum MB of the atomic weights and the sum MA of the atomic weights of the atoms contained in the portion A of the organic layer satisfy the relationship of the following formula (I), and the sum MB of the atomic weights is 1 / of the molecular weight of the hole injection material. Having a portion B greater than 3;
The solubility parameter SA of the part A and the solubility parameter SB of the part B satisfy the relationship of the following formula (II).
| MA-MB | / MB ≦ 2 Formula (I)
| SA-SB | ≦ 2 Formula (II)

  When the relationship between the SP value of the part B of the compound contained in the organic layer and the part A of the hole injection material satisfies the relational expression (I), the molecular polarity matching between the part A and the part B is good. Therefore, the physical adhesion stability of both portions is high, and the adhesion at the interface between the hole injection layer and the hole transport layer can be kept stable, which contributes to a longer driving life of the organic device. In addition, since the hole injection material has a linking group connected to an electrode (hole injection electrode) on which the hole injection material is laminated, adhesion at the interface between the hole injection layer and the electrode is stabilized. This contributes to a longer driving life of the organic device.

Hereinafter, the layer structure of the organic device according to the present invention will be described.
FIG. 1 is a conceptual cross-sectional view showing the basic layer structure of an organic device according to the present invention. The basic layer structure of the organic device of the present invention is such that a hole injection layer 2, an organic layer 3, and an electrode 6 are laminated on the surface of an electrode 1 provided on a substrate 7.
The board | substrate 7 is a support body for forming each layer which comprises an organic device, and does not necessarily need to be provided in the surface of the electrode 1, and should just be provided in the outermost surface of the organic device.

The hole injection layer 2 contains a hole injection material and has a role of assisting hole injection from the electrode 1 to the organic layer 3.
The organic layer 3 is a layer that exhibits various functions depending on the type of device by hole injection, and may be composed of a single layer or a multilayer. In the case where the organic layer is composed of multiple layers, the organic layer is referred to as a layer that serves as the center of the function of the organic device (hereinafter referred to as a functional layer) and an auxiliary layer of the functional layer (hereinafter referred to as an auxiliary layer). ) Is included. For example, in the case of an organic EL element, a hole transport layer stacked on the surface of the hole injection layer corresponds to the auxiliary layer, and a light emitting layer stacked on the surface of the hole transport layer corresponds to the functional layer.
The electrode 6 is provided at a place where the hole injection layer 2 and the organic layer 3 exist between the electrode 1 and the electrode 6 facing each other. Moreover, you may have the 3rd electrode which is not shown in figure as needed. By applying an electric field between these electrodes, the function of the organic device can be expressed.

FIG. 2 is a schematic cross-sectional view showing an example of a layer configuration of an organic EL element which is an embodiment of the organic device according to the present invention. The organic EL device of the present invention has a configuration in which a hole transport layer 4 as an auxiliary layer and a light emitting layer 5 as a functional layer are laminated on the surface of the hole injection layer 2. The electrode 1 functions as an anode and the electrode 6 functions as a cathode.
In the organic EL device, when an electric field is applied between the anode and the cathode, holes are injected from the anode into the light emitting layer 5 through the hole injection layer 2 and the hole transport layer 4, and electrons are emitted from the cathode. By being injected into the layer, the holes and electrons injected inside the light emitting layer 5 are recombined to have a function of emitting light to the outside of the device.
In order to emit light to the outside of the element, all the layers existing on at least one surface of the light emitting layer need to be transparent to light having at least a part of wavelengths in the visible wavelength range. Further, an electron transport layer and / or an electron injection layer may be provided between the light emitting layer and the electrode 6 (cathode) as required (not shown).

FIG. 3 is a schematic cross-sectional view showing an example of the layer structure of an organic transistor which is another embodiment of the organic device according to the present invention. The organic transistor is disposed on a substrate 7 between the electrode 9 (gate electrode), the opposing electrode 1 (source electrode) and electrode 6 (drain electrode), and the electrode 9, electrode 1, and electrode 6. An organic semiconductor layer 8 as an organic layer, and an insulating layer 10 interposed between the electrode 9 and the electrode 1 and between the electrode 9 and the electrode 6, and the hole injection layer 2 on the surface of the electrode 1 and the electrode 6 Is formed.
The organic transistor has a function of controlling a current between the source electrode and the drain electrode by controlling charge accumulation in the gate electrode.

  The layer structure of the organic device of the present invention is not limited to the above examples, and has substantially the same structure as the technical idea described in the claims of the present invention, and has the same function. Anything that has an effect is included in the technical scope of the present invention.

Hereinafter, each layer of the organic device according to the present invention will be described in detail.
(1) Hole injection layer and organic layer

The organic layer contained in the organic device of the present invention is laminated on the surface of the hole injection layer, and contains, as a constituent component, a compound containing a part A having a total atomic weight MA of 100 or more as a part of the chemical structure. In the present invention, the sum of atomic weights means the sum of atomic weights of all atoms contained in a part of the molecule.
Part A is a part that has a major influence on the physical adhesion stability of the interface between the organic layer and the hole injection layer in the molecule of the compound contained in the organic layer. It is considered that the sum MA of the atomic weights of the portion A is 100 or more in order to sufficiently affect the physical adhesion stability at the interface between the hole injection layer and the organic layer. MA is preferably 150 or more, particularly preferably 200 or more.

  When an organic layer consists of a multilayer, the compound containing the said part B is contained in the layer adjacent to a positive hole injection layer among the layers contained in an organic layer. For example, in the case of the organic EL device shown in FIG. 2, the compound containing the portion A is included in the hole transport layer 4 that is the layer closest to the hole injection layer 2. In the case of the organic transistor shown in FIG. 3, the organic transistor is included in the organic semiconductor layer 8 that is the layer closest to the hole injection layer 2.

  When two or more parts A are contained in one molecule of the compound, for example, when the compound contained in the organic layer is a polymer compound having a repeating unit, the atomic weight of the atoms contained in the plurality of parts A The total is preferably larger than 1/3 of the molecular weight of the compound having the portion A from the viewpoint of further improving the adhesion stability at the interface between the hole injection layer and the organic layer, and more preferably 2/5 or more, particularly 3 / 5 or more is preferable.

  On the other hand, the hole injection layer included in the organic device of the present invention has a function in which the hole injection material included in the layer is connected to the electrode on which the hole injection material is laminated as a part of its chemical structure. The resulting linking group and the sum MB of atomic weights are 100 or more, and the sum MB of the atomic weights and the sum MA of the atomic weights of atoms contained in the portion A of the organic layer satisfy the relationship of the following formula (I), The sum B of atomic weights has a portion B that is larger than 1/3 of the molecular weight of the hole injection material.

In the hole injection layer, the hole injection material is presumed that molecules are arranged with the linking group mainly directed toward the hole injection electrode. In this way, the molecules of the hole injection material are regularly arranged on the electrode, whereby a monomolecular film or a thin film having a thickness of several molecules is formed. Here, the linking group is a group that causes an action of linking to the hole injection electrode, and the linking is presumed to be due to physical adsorption or a chemical bond is formed. For the hole injection electrode, a metal oxide such as ITO or a metal is usually used. In the case of a metal oxide, an electron is attracted to an oxygen atom having a large electronegativity at a site of a metal (Me) oxygen (O) bond, and the polarity locally exists in the Me-O bond portion. In some cases, oxygen atoms are terminated with hydrogen (H), and there is a large polarity of Me—O—H. And even in the case of metal, unless the surface is deposited and stored under an ultrahigh vacuum of 10 ⁻⁸ Pa or higher, the metal is oxidized or hydroxylated on the outermost surface even in vacuum. It is said. In the case of physical adsorption, the polar group on the electrode surface and the polar part of the P—Cl bond or PO bond of the compound represented by the general formula (3), for example, are attracted by van der Waals force, and molecules are attracted to the electrode surface. Presumed to be adsorbed (Non-Patent Document 2). In the case of chemical bonding, it is presumed that a Me—OP bond is formed by a chemical reaction between the electrode surface and the compound represented by the general formula (3).
In this way, the hole injection material has a linking group with the electrode, and the hole injection material is arranged in the hole injection layer in such a direction that the linking group can be connected to the hole injection electrode. The adhesion stability at the injection electrode-hole injection layer interface is improved.

On the other hand, the portion B is a portion that has a major influence on the physical adhesion stability of the hole injection layer-organic layer interface in the molecule of the hole injection material. In the hole injection material (1), the X portion is mainly directed toward the hole transport material, and the connection between the hole transport material and the hole injection material is considered to be physical adsorption by van der Waals force or the like. Since the SP value is close or similar, the adhesion between the hole injection layer and the hole transport layer is kept stable. Therefore, the part B needs a skeleton having a certain size, and the sum MB of the atomic weight of the part B is 100 or more and that the molecular weight of the hole injection material is larger than 1/3. It is considered necessary in order to sufficiently influence the physical adhesion stability at the interface between the hole injection layer and the organic layer in the molecule of the material.
MB is preferably 100 or more, particularly 150 or more, and more preferably 2/5 or more, particularly 3/5 or more, of the molecular weight of the hole injection material.
In addition, both parts are such that the relationship between the sum MB of the atomic weight of the part B contained in the hole injection material and the sum MA of the atomic weight of the part A contained in the compound contained in the organic layer satisfies the above formula (I). Materials with the same difference in the sum of the atomic weights are used. The smaller the difference between MA and MB, the better. The value of | MA-MB | / MB is preferably 1 or less, and more preferably 0.5 or less.

In addition, for the parts A and B where the sums MA and MB of the atomic weight satisfy the above conditions, the solubility parameter SA of the part A and the solubility parameter SB of the part B satisfy the relationship of the following formula (II).
| SA-SB | ≦ 2 Formula (II)

  The solubility parameter (hereinafter sometimes referred to as SP value) is an index indicating the compatibility and incompatibility between substances, and is an index related to the polarity of the group in the molecule. If the difference in SP value between the two substances in contact is small, the difference in polarity between the two molecules is also small. In this case, the cohesive force between the two substances is close, so the compatibility and solubility are large and the solubility becomes high, and the adhesion stability of the interface, that is, the contact area is kept stable. On the other hand, if the difference in SP value is large, the difference in cohesive force between the two substances is also large. In this case, the compatibility and solubility are small, and it is hardly soluble or insoluble, the adhesion of the interface is unstable, and the interface changes so as to reduce the contact area between the two substances.

There are several methods for measuring and calculating the SP value. In the present invention, Bicerano's method [Prediction of polymer properties, Marcel Decker Inc. , New York (1993)]. In the Bicerano method, the solubility parameter of a polymer is obtained by an atomic group contribution method.
If not obtained from this document, other known documents such as the method of Fedors [Fedors, R .; F. , Polymer Eng. Sci. , 14, 147 (1974)] or the method of Askadskii [A. A. Askadaskii et al. , Vysokomol. Soyed. , A19, 1004 (1977). ] Can be used. In the Fedors method, the solubility parameter of a polymer is obtained by the atomic group contribution method. In the atomic group contribution method, a molecule is divided into several atomic groups, and empirical parameters are assigned to each atomic group to determine the total molecular weight. This is a method for determining physical properties.

The molecular solubility parameter δ is defined by the following equation.
δ≡ (δ _d ² + δ _p ² + δ _h ² ) ^1/2
Here, δ _d is a London dispersion force term, δ _p is a molecular polarization term, and δ _h is a hydrogen bond term.
Each term is calculated by the following formula using the molar attractive force multiplier (F _di , F _p i, E _hi ) and the molar volume Vi of each term of the constituent atomic group i of the molecule.

δ _d ² = ΣF _d i / ΣVi
δ _p ² = (ΣF _p i ² ) ^1/2 / ΣVi
δ _h ² = (ΣE _h i / ΣVi) ^1/2

The numerical values listed in the three-dimensional solubility parameter calculation table shown in Table 1 are used as the molar attractive force multipliers ( _Fd i, F _p i, E _h i) and molecular volume Vi of each term of the constituent atomic group i. For atomic groups not listed in this table, the molar attraction multipliers (F _d i, F _p i, E _h i) of each term are values based on van Krevelen (the following documents A and B), and the molar volume Vi Uses the value by Fedors (reference C).

Literature A: KEMeusburger: "Pesticide Formulations: Innovations and Developments" Chapter 14 (Am. Chem. Soc.), 151-162 (1988)
Reference B: AFMBarton: "Handbook of Solubility Parameters and Other Cohesion Parameters" (CRC Press Inc., Boca Raton, FL) (1983)
Literature C: RFFedors: Polymer Eng. Sci., 14, (2), 147-154 (1974)

  In addition, as an experimental evaluation method for evaluating the wettability and SP value of an organic surface, there is a contact angle measurement method using a solvent, etc., but such a macro measurement method evaluates the averaged wettability. Will do. Therefore, the method based on the above calculation is desirable as a method for evaluating wettability and adhesion stability in the length order of nm scale.

  Since the difference in SP value between the part A of the compound contained in the organic layer and the part B of the hole injection material is small, the compatibility between the compound contained in the organic layer and the hole injection material is increased. The adhesion stability at the interface between the layer and the organic layer is improved. The difference between SA and SB represented by the above formula (II) is preferably 1 or less, and more preferably 0.5 or less.

  As the compound and the hole injection material contained in the organic layer of the present invention, any material may be used as long as it satisfies the requirements of the present invention, and can be arbitrarily specified.

  In the organic layer, the content of the compound containing the portion A is 50% by weight or more, more preferably 70% by weight or more, and particularly 90% by weight or more. The hole injection layer preferably has a molecular size (nm) in which the content of the hole injection material containing the portion B is 50% by weight or more, more preferably 70% by weight or more, particularly 90% by weight or more. From the viewpoint of the adhesion stability of the length scale of the order).

The organic device according to the present invention has improved adhesion stability at the hole injection electrode-hole injection layer interface and the hole injection layer-organic layer interface, so that the adhesion stability is maintained even when the organic device is used for a long time. Can be driven in a stable state.
When the sum MA of the atomic weights of the atoms contained in the part A is less than 100, the hole injection material having no linking group is used, or when the sum of the atomic weights of the atoms contained in the part B is less than 100, If the total MB of the atomic weight of the atoms contained in the part B is not more than 1/3 of the molecular weight and / or the SP value is outside the range of the above formula (II), the lifetime of the device is short. There are many cases. It is presumed that driving of an organic device for a long time causes nano-order level peeling at the interface between the hole injection layer and the hole transport layer, resulting in deterioration of the performance of the organic device.

In the organic device of the present invention, the hole injection layer preferably contains a hole injection material represented by the following general formula (1).
XY (1)
However, X is a part including the part B and ensuring adhesion stability with the organic layer. Y is a connecting group connected to the electrode.

  By providing the hole injection layer containing the hole injection material represented by the general formula (1) on the hole injection electrode, the adhesion between the electrode and the organic semiconductor material is stably maintained, and the long drive life of the organic device is achieved. Contributes to

In Formula (1), the portion B contained in X improves the adhesion stability with the organic layer.
On the other hand, Y is a linking group that can be connected to an electrode. The number of linking groups contained in one molecule of the hole injection material may be any number as long as it is one or more. However, when two or more of the linking groups are present in one molecule, the hole injection materials are polymerized so that the linking group portion that is incompatible with the organic layer material is exposed at the organic layer side interface, There is a possibility of hindering the adhesion stability between the hole injection layer and the organic layer. Therefore, it is preferable that there is one linking group in one molecule of the hole injection material. When the number of linking groups is one in one molecule, the hole injection material binds to the substrate or forms a dimer by a bimolecular reaction and stops the reaction. Since the dimer has poor adhesion to the substrate, it can be easily removed from the film by applying a washing step.
The linking group Y is a group containing at least an oxygen atom and a halogen atom, and is preferably selected from the following groups represented by the following formula (4).

In formula (4), Z1, Z2 and Z3 each independently represent a halogen atom or an alkoxy group, and a chlorine atom, a methoxy group and an ethoxy group are particularly preferred. These linking groups Y are usually linked to the surface of the hole injection electrode by linking to a reactive functional group (in many cases, a hydroxyl group) present on the surface of the hole injection electrode. Among them, the linking group Y is preferably a phosphate chloride group (—OP (═O) Cl ₂ ) from the viewpoint that adhesion stability is improved and life is improved.

The hole injection layer and the organic layer may have a portion A of the compound contained in the organic layer of the present invention having the same skeleton as the portion B of the hole injection material or a similar skeleton including a spacer structure in the same skeleton. It is preferable from the viewpoint of improving the adhesion stability of the interface and contributing to a longer driving life. The skeleton means a structure in which a substituent is removed from the part A or the part B. Here, including a spacer structure means that an atom that extends the skeleton is present. The atoms that extend the skeleton are preferably hydrocarbon structures having 1 to 12 carbon atoms, but may contain other atoms such as an ether bond.
Specific examples of the skeleton that the part A and the part B have in common include, for example, triphenylamine skeleton, fluorene skeleton, biphenyl skeleton, pyrene skeleton, anthracene skeleton, carbazole skeleton, phenylpyridine skeleton, trithiophene skeleton, phenyl oxadi Examples thereof include an azole skeleton, a phenyltriazole skeleton, a benzimidazole skeleton, a phenyltriazine skeleton, a benzodiathiazine skeleton, a phenylquinoxaline skeleton, a phenylene vinylene skeleton, a phenylsilole skeleton, and a skeleton formed by combining these skeletons.
As long as the part A and the part B have the same or similar skeleton, the type, number, and position of substituents on the skeleton may be different. When having a substituent on the skeleton, the type is preferably, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, and further a linear or branched alkyl group having 1 to 12 carbon atoms, such as methyl. Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group Etc. are preferred.

  Two or more kinds of the compound portion A contained in the organic layer and the hole injection material portion B contained in the hole injection layer may exist in one molecule. In this case, the ratio of the common part in the whole hole injection layer is increased, and the adhesion stability of the interface is improved.

  Further, in the case where the hole injection material is a compound represented by the general formula (1), the total atomic weight MB of atoms contained in the portion B is equal to (from 1/3 of the total atomic weight of atoms contained in X) Is larger than 2/5, more preferably 3/5 from the viewpoint of further improving the adhesion stability at the interface between the hole injection layer and the organic layer and contributing to a longer driving life.

  When a polymer compound having one type or two or more types of repeating units is used as the compound contained in the organic layer, usually one type or two or more types are selected from the repeating units, and the portion A (part A is When two or more types are included, the portion A, A ′, A ″, etc.) is used, and the hole injection material included in the hole injection layer is the same skeleton as the portion A or a spacer structure in the same skeleton. A hole injection material having a portion B having a similar skeleton including (when there are two or more types of portions B, portions B, B ′, B ″, etc. corresponding to two or more types of portions A) is used.

  For example, when the material contained in the organic layer is a compound represented by the following general formula (2), a compound represented by the following general formula (3) can be suitably used as the hole injection material.

(However, Ar _{1 to} Ar ₄ may be the same as or different from each other, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 60 carbon atoms related to the conjugated bond, or An unsubstituted or substituted heterocyclic group having 4 or more and 60 or less carbon atoms related to a conjugated bond is shown, n is 0 to 10,000, m is 0 to 10,000, and n + m = 1 to 20,000. The arrangement of the two repeating units is arbitrary.)

(However, Ar _{5 to} Ar ₇ may be the same as or different from each other, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 60 carbon atoms related to the conjugated bond, or An unsubstituted or substituted heterocyclic group having 4 to 60 carbon atoms with respect to a conjugated bond is shown.)

In Ar _{1 to} Ar ₄ and Ar _{5 to} Ar ₇ , specific examples of the aromatic hydrocarbon in the aromatic hydrocarbon group include benzene, fluorene, naphthalene, anthracene, and combinations thereof, and combinations thereof. Derivatives, further phenylene vinylene derivatives, styryl derivatives and the like. Specific examples of the heterocyclic ring in the heterocyclic group include thiophene, pyridine, pyrrole, carbazole, combinations thereof, and derivatives thereof.

In the general formula (2) and the general formula (3), a combination of Ar ₁ , Ar ₂ , and Ar _{3 is} a combination of Ar ₅ , Ar ₆ , and Ar ₇ , and at least an aromatic hydrocarbon group or a heterocyclic group. The skeletons of are preferably the same. When Ar _{1 to} Ar _{4 in} the general formula (2) have a substituent, the substituent is a linear or branched alkyl group or alkenyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. Group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, vinyl group, allyl group Etc. When Ar _{5 to} Ar _{7 in} the general formula (3) have a substituent, the substituent includes a fluorene skeleton, a biphenyl skeleton, a pyrene skeleton, and an anthracene skeleton in addition to a linear or branched alkyl group having 1 to 12 carbon atoms. , Carbazole skeleton, phenylpyridine skeleton, trithiophene skeleton, phenyloxadiazole skeleton, phenyltriazole skeleton, benzimidazole skeleton, phenyltriazine skeleton, benzodiathiazine skeleton, phenylquinoxaline skeleton, phenylene vinylene skeleton, phenylsilole skeleton, etc. And monovalent or divalent groups obtained by removing hydrogen from one or two carbon positions of the aromatic hydrocarbon ring or heterocyclic ring. The monovalent or divalent group obtained by removing hydrogen from one or two carbon positions of the aromatic hydrocarbon ring or heterocyclic ring may further have a substituent such as an alkyl group.
Among these, the compound represented by the general formula (3) preferably has a structure represented by the following general formula (3 ′) from the viewpoint of improving adhesion stability due to the commonality of the structure with the formula (2). .

（但し、Ａｒ_５〜Ａｒ_８は、相互に同一であっても異なっていてもよく、共役結合に関する炭素原子数が６個以上６０個以下からなる未置換もしくは置換の芳香族炭化水素基、または共役結合に関する炭素原子数が４個以上６０個以下からなる未置換もしくは置換の複素環基を示す。ｑは０〜１０、ｒは１〜１０であり、ｑ＋ｒ＝１〜２０である。また、２つの繰り返し単位の配列は任意である。）
一般式（３’）におけるＡｒ_８も、具体的には、一般式（３）のＡｒ_５〜Ａｒ_７と同様のものが好適に用いられる。上記一般式（２）及び一般式（３’）において、Ａｒ_１、Ａｒ_２、及びＡｒ_３の組み合わせは、Ａｒ_５、Ａｒ_６、及びＡｒ_７の組み合わせと、また、Ａｒ_４は、Ａｒ_８と、少なくとも芳香族炭化水素基または複素環基の骨格が同一であることが好ましい。

(However, Ar _{5 to} Ar ₈ may be the same as or different from each other, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 60 carbon atoms related to the conjugated bond, or An unsubstituted or substituted heterocyclic group having 4 to 60 carbon atoms with respect to a conjugated bond is shown, q is 0 to 10, r is 1 to 10, and q + r = 1 to 20. The arrangement of the two repeating units is arbitrary.)
Specifically, Ar ₈ in the general formula (3 ′) is also preferably the same as Ar _{5 to} Ar _{7 in} the general formula (3). In the general formula (2) and the general formula (3 ′), a combination of Ar ₁ , Ar ₂ , and Ar _{3 is} a combination of Ar ₅ , Ar ₆ , and Ar ₇ , and Ar ₄ is Ar ₈ and It is preferable that at least the skeletons of the aromatic hydrocarbon group or the heterocyclic group are the same.

Specifically, the compound represented by the general formula (2) is poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4) represented by the following formula (5). '-(N- (4-sec-butylphenyl)) diphenylamine)] (TFB), the hole injection material is diphenylaminophenyl phosphate dichlorophosphodate (TPA-OP (2) represented by the following formula (6): O) Cl ₂ ) or a compound represented by the following formulas (7) to (10), the interface between the hole injection layer and the hole injection electrode, and the interface between the hole injection layer and the hole transport layer In particular, the stability of adhesion can be maintained, and the stability of the adhesion can be maintained. R each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an aryloxy group having 6 to 60 carbon atoms, or 7 to 7 carbon atoms. A group selected from the group consisting of 60 arylalkyls, C7-C60 arylalkoxy groups, C4-C60 heterocyclic groups, cyano groups, nitro groups, and halogen atoms.

  For example, when PVK (polyvinylcarbazole) is used for the hole transport layer, compounds represented by the following formulas (11) to (13) can be suitably used as the hole injection material. Here, R is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an aryloxy group having 6 to 60 carbon atoms, or a carbon number. A group selected from the group consisting of 7 to 60 arylalkyls, C7 to C60 arylalkoxy groups, C4 to C60 heterocyclic groups, cyano groups, nitro groups, and halogen atoms.

  The organic layer may contain additives such as a binder resin, a curable resin, and a coating property improving agent as necessary. Examples of the binder resin include polycarbonate, polystyrene, polyarylate, and polyester. Moreover, you may contain the binder resin hardened | cured with a heat | fever or light. Thus, when the organic layer forming coating liquid is applied, elution of the constituent components of the organic layer with respect to the underlying layer to which the coating liquid is applied, for example, in the case of an organic EL element, the constituent components of the hole transport layer Elution can be reduced. As a material that is cured by heat or light, a material in which a curable functional group is introduced into the molecule in the light emitting layer material, a curable resin, or the like can be used. Specifically, examples of the curable functional group include acrylic functional groups such as acryloyl group and methacryloyl group, vinylene group, epoxy group, and isocyanate group. The curable resin may be a thermosetting resin or a photocurable resin, and examples thereof include an epoxy resin, a phenol resin, a melamine resin, a polyester resin, a polyurethane resin, a silicon resin, and a silane coupling agent. be able to. When the curable resin is used, as described above, the light emitting layer can be obtained by dispersing the light emitting material in the curable resin using the curable resin as a binder.

The thickness of the hole injection layer is preferably from 0.1 to 100 nm, particularly preferably from 0.1 to 20 nm, from the viewpoint of hole injection efficiency. More preferably, the film thickness is the molecular length of the hole injection material.
The work function of the hole injection layer is preferably 5.0 to 6.0 eV, more preferably 5.0 to 5.8 eV, from the viewpoint of hole injection efficiency.

  Since the hole injection layer is formed by a solution coating method, when the coating solution is applied onto the substrate, the linking group of the hole injection material is selectively connected to the substrate. It is preferable from the point that it is difficult to contain impurities contained in the coating solution, and a hole injection layer excellent in adhesion stability at the interface and hole injection efficiency can be formed.

The organic layer may be formed on the hole injection layer by a solution coating method. When the coating solution is applied onto the hole injection layer, the portion B of the hole injection material is formed. And the portion A of the organic layer are selectively connected, which is preferable from the viewpoint that it is difficult to contain impurities contained in the coating solution, and an organic layer having excellent adhesion stability at the interface and excellent electrical characteristics can be formed.
The solution coating method will be described below in the item of manufacturing method of organic device.

(2) Substrate The substrate is a support for the organic device of the present invention, and may be a flexible material or a hard material, for example. Specific examples of materials that can be used include glass, quartz, polyethylene, polypropylene, polyethylene terephthalate, polymethacrylate, polymethyl methacrylate, polymethyl acrylate, polyester, and polycarbonate.
Among these, when a synthetic resin substrate is used, it is desirable to have a gas barrier property. Although the thickness of a board | substrate is not specifically limited, Usually, it is about 0.5-2.0 mm.

(3) Electrode The organic device of this invention has two or more electrodes which oppose on a board | substrate.
In the organic device of the present invention, the electrode is preferably formed of a metal or a metal oxide, for example, platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, Tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, indium tin oxide (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon paste, lithium , Beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium-potassium alloy, magnesium, lithium, aluminum, magnesium / copper mixed , Magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide mixture, lithium / aluminum mixture, etc., but usually metals such as aluminum, gold, silver, nickel, palladium, platinum, indium And / or metal oxides such as tin oxide.

The electrode is usually often formed on the substrate by a method such as sputtering or vacuum deposition, but can also be formed by a wet method such as a coating method or a dipping method. The thickness of the electrode varies depending on the transparency required for each electrode. When transparency is required, the light transmittance in the visible light wavelength region of the electrode is usually 60% or more, preferably 80% or more. In this case, the thickness is usually 10 to 1000 nm, Preferably, it is about 20 to 500 nm.
In the present invention, a metal layer may be further provided on the electrode in order to improve the adhesion stability with the charge injection material according to the present invention. The metal layer refers to a layer containing metal, and is formed from the metal or metal oxide used in the normal electrode as described above.

(4) Others The organic device of the present invention may have a conventionally known electron injection layer and / or electron transport layer between the electron injection electrode and the organic layer as necessary.

2. Organic EL device

As one Embodiment of the organic device of this invention, the organic EL element in which an organic layer contains a positive hole transport layer and a light emitting layer at least is mentioned.
Hereinafter, each layer which comprises an organic EL element is demonstrated in order using FIG.
(substrate)
The substrate 7 becomes a support for the organic EL element, and may be a flexible material or a hard material, for example. Specifically, for example, those mentioned in the description of the substrate of the organic device can be used.
When the light emitted from the light emitting layer 5 is extracted through the substrate 7 side, at least the substrate 7 needs to be made of a transparent material.

(Anode, cathode)
The electrode 1 and the electrode 6 differ depending on the direction in which the light emitted from the light emitting layer 5 is extracted. Which electrode is required to have transparency or not, the electrode 1 is transparent when the light is extracted from the substrate 7 side. It is necessary to form the electrode 6 with a transparent material.
The electrode 1 provided on the light emitting layer side of the substrate 7 acts as an anode for injecting holes into the light emitting layer, and the electrode 6 provided on the light emitting layer side of the substrate 7 injects electrons into the light emitting layer 5. Acting as a cathode.
In the present invention, the anode and the cathode are preferably formed of the metals or metal oxides listed in the description of the electrode of the organic device.

(Hole injection layer and hole transport layer)
The hole injection layer 2 and the hole transport layer 4 are formed on the surface of the electrode 1 between the light emitting layer 5 and the electrode 1 (anode) as shown in FIG. In the organic EL element of the present invention, the organic layer closest to the hole injection layer is a hole transport layer, and the relationship between the hole injection layer and the organic layer described in the description of the organic device is the organic EL element. This can be applied to the relationship between the hole injection layer 2 and the hole transport layer 2 in FIG.
It is positive that the hole transport material contained in the hole transport layer is a compound represented by the general formula (2), and the hole injection material is a compound represented by the general formula (3). This is preferable from the viewpoint of improving the adhesion stability of the interface between the hole injection layer and the hole transport layer and contributing to a longer driving life.

Among the combinations of the hole transport material and the hole injection material represented by the above formulas (2) and (3), the hole transport material is a TFB represented by the above formula (5), and the hole injection material Is TPA-OP (O) Cl ₂ represented by the above formula (6), the interface between the hole injection layer and the hole injection electrode and the interface between the hole injection layer and the hole transport layer are particularly It is particularly preferable in that it can be stabilized and adhesion stability can be maintained, and it can greatly contribute to driving stability and a long driving life of the organic EL element.

  Furthermore, in consideration of hole injection characteristics, a hole injection material and a hole transport material in which the work function (HOMO) value of each layer increases stepwise from the electrode 1 toward the light emitting layer 5 that is an organic layer. It is preferable that the hole injection energy barrier at each interface be made as small as possible to complement the large hole injection energy barrier between the electrode 1 and the light emitting layer 5.

Specifically, for example, when ITO (work function 5.0 eV immediately after UV ozone cleaning) is used for the electrode 1 and Alq3 (HOMO 5.7 eV) is used for the light emitting layer 5, TPA is used as a material constituting the hole injection layer. —OP (O) Cl ₂ (work function 5.3 eV), TFB (work function 5.4 eV) as the material constituting the hole transport layer, and each layer from the electrode 1 side toward the light emitting layer 5 It is preferable to arrange the layers so that the values of the work functions increase in order. At this time, the first layer, the second layer, etc. may be either a monomolecular film or a film in which molecules are stacked in multiple layers. In addition, the value of the said work function or HOMO was quoted from the measured value of the photoelectron spectroscopy which used photoelectron spectrometer AC-1 (made by Riken Keiki).
In the case of such a layer structure, a large energy barrier of hole injection between the electrode 1 (work function 5.0 eV immediately after UV ozone cleaning) and the light-emitting layer 5 (for example, HOMO 5.7 eV), the HOMO value is stepped. As a result, a hole injection layer having excellent hole injection efficiency can be obtained.

  However, it is not always necessary to arrange the metal work function so that the value of the work function of the metal increases from the electrode 1 side toward the light emitting layer 5 that is an organic layer. There is. In particular, in the present invention, when the hole injection layer is a single molecule or a few molecules of about 1-2 nm, holes can be injected by the tunnel effect even if the HOMO value does not satisfy the above preferable conditions. Furthermore, a long life characteristic is expected due to the effect that the hole injection layer improves the adhesion stability between the electrode and the hole transport layer.

  The hole transport layer can be formed by the same method as the light emitting layer described later, using the hole transport material. The film thickness of the hole transport material is usually 0.1 to 1000 nm, preferably 1 to 500 nm.

(Light emitting layer)
As shown in FIG. 2, the light emitting layer 5 is formed of a light emitting material between the substrate 7 on which the electrode 1 is formed and the electrode 6.

  The material used for the light emitting layer of the present invention is not particularly limited as long as it is a material usually used as a light emitting material, and either a fluorescent material or a phosphorescent material can be used. Specifically, materials such as a dye-based light emitting material and a metal complex-based light emitting material can be given, and either a low molecular compound or a high molecular compound can be used.

(Specific examples of dye-based luminescent materials)
Examples of dye-based light-emitting materials include arylamine derivatives, anthracene derivatives, (phenylanthracene derivatives), oxadiazole derivatives, oxazole derivatives, oligothiophene derivatives, carbazole derivatives, cyclopentadiene derivatives, silole derivatives, distyrylbenzene derivatives, Distyrylpyrazine derivatives, distyrylarylene derivatives, silole derivatives, stilbene derivatives, spiro compounds, thiophene ring compounds, tetraphenylbutadiene derivatives, triazole derivatives, triphenylamine derivatives, trifumanylamine derivatives, pyrazoloquinoline derivatives, hydrazone derivatives, pyras Examples include zoline dimer, pyridine ring compound, fluorene derivative, phenanthroline, perinone derivative, perylene derivative. These dimers, trimers, oligomers, and compounds of two or more derivatives can also be used.

Specifically, as a triphenylamine derivative, N, N′-bis- (3-methylphenyl) -N, N′-bis- (phenyl) -benzidine (TPD), 4,4,4-tris (3 -Methylphenylphenylamino) triphenylamine (MTDATA), bis (N- (1-naphthyl-N-phenyl) benzidine) (α-NPD) as arylamines, (2- (4 -Biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole) (PBD), as an anthracene derivative, 9,10-di-2-naphthylanthracene (DNA), as a carbazole derivative 4,4-N, N′-dicarbazole-biphenyl (CBP), 1,4-bis (2,2-diphenylvinyl) benzene (DPVBi) Specific examples of enanthrolines include bathocuproin and bathophenanthroline. These materials may be used alone or in combination of two or more.

(Specific examples of metal complex light emitting materials)
Examples of metal complex light emitting materials include aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethylzinc complex, porphyrin zinc complex, europium complex, etc., or central metal such as Al, Zn, Be, etc. Alternatively, a metal complex having a rare earth metal such as Tb, Eu, or Dy and having a oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure, or the like as a ligand can be given.
Specifically, tris (8-quinolinolato) aluminum complex (Alq3), bis (2-methyl-8-quinolinato) (p-phenylphenolate) aluminum complex (BAlq), tri (dibenzoylmethyl) phenanthroline europium complex, Bis (benzoquinolinolato) beryllium complex (BeBq) can be mentioned. These materials may be used alone or in combination of two or more.

(Polymer-based luminescent materials)
As the high molecular weight light emitting material, a material obtained by introducing the above low molecular weight material into the molecule as a straight chain, a side chain or a functional group, a polymer, a dendrimer, or the like can be used.
Examples thereof include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyvinyl carbazole, polyfluorenone derivatives, polyfluorene derivatives, polyquinoxaline derivatives, and copolymers thereof.

(Specific examples of dopant)
A doping material may be added to the light emitting layer for the purpose of improving the light emission efficiency or changing the light emission wavelength. In the case of a polymer material, these may be included as a luminescent group in the molecular structure. Examples of such doping materials include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacdrine derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazoline derivatives, decacyclene, phenoxazone, quinoxaline derivatives, carbazole derivatives, and fluorene derivatives. Can be mentioned. Moreover, the compound which introduce | transduced the spiro group into these can also be used.
Specifically, 1-tert-butyl-perylene (TBP), coumarin 6, Nile red, 1,4-bis (2,2-diphenylvinyl) benzene (DPVBi), 1,1,4,4-tetraphenyl -1,3-butadiene (TPB). These materials may be used alone or in combination of two or more.
As a phosphorescent dopant, an organometallic complex having a heavy metal ion such as platinum or iridium at the center and exhibiting phosphorescence can be used. Specifically, Ir (ppy) ₃ , (ppy) ₂ Ir (acac), Ir (BQ) ₃ , (BQ) ₂ Ir (acac), Ir (THP) ₃ , (THP) ₂ Ir (acac), Ir (BO) ₃ , (BO) ₂ (acac), Ir (BT) ₃ , (BT) ₂ Ir (acac), Ir (BTP) ₃ , (BTP) ₂ Ir (acac), FIr6, PtOEP, or the like is used. be able to. These materials may be used alone or in combination of two or more.

In the present invention, as the material of the light emitting layer, any of a low molecular compound or a high molecular compound that emits fluorescence or a low molecular compound or a high molecular compound that emits phosphorescence can be used. In the present invention, in the case where the charge injection layer is formed using the charge injection material according to the present invention, since many of the charge injection layers can be formed by application using an alcohol solvent, xylene is used as the material of the light emitting layer. It is possible to use a polymer type material that easily dissolves in a non-aqueous solvent such as a layer and forms a layer by a solution coating method. In this case, a high molecular compound containing a fluorescent compound or a low molecular compound that emits fluorescence, or a high molecular compound containing a phosphor compound or a low molecular compound that emits phosphor can be preferably used.
The light emitting layer can be formed using a light emitting material by a solution coating method, a vapor deposition method, or a transfer method. The solution coating method will be described below in the item of manufacturing method of organic device. For example, in the case of the vacuum evaporation method, the material of the light emitting layer is put in a crucible installed in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 ⁻⁴ Pa by an appropriate vacuum pump. Is heated to evaporate the material of the light emitting layer, and the light emitting layer 5 is formed on the laminate of the substrate 7, the electrode 1, the hole injection layer 2, and the hole transport layer 4 placed facing the crucible. . In the transfer method, for example, a light emitting layer previously formed on a film by a solution coating method or a vapor deposition method is bonded to a hole transport layer provided on an electrode, and the light emitting layer is transferred to the hole transport layer by heating. It is formed. Alternatively, the hole transport layer side of the laminate that is laminated in the order of the film, the light emitting layer, and the hole transport layer may be transferred to the electrode.
The thickness of the light emitting layer is usually about 1 to 500 nm, preferably about 20 to 1000 nm. Since the present invention is characterized in that the hole injection material is formed by a wet coating method, there is an advantage that the process cost can be reduced when the light emitting layer is formed by a coating process. Furthermore, when the light emitting layer is formed by a coating process, a heating process for drying the solvent may be required. However, since the SP values of the hole injection layer and the hole transport layer are close, the interface is caused by molecular movement due to heating. The contact area of the length scale of the order of nm does not decrease and the adhesion stability does not deteriorate.

3. Organic Transistor Another embodiment of the organic device according to the present invention is an organic transistor. Hereinafter, each layer which comprises an organic transistor is demonstrated using FIG.
In the organic transistor according to one embodiment of the present invention, the organic layer closest to the hole injection layer is an organic semiconductor layer, and the hole injection layer and the hole transport layer described in the description of the organic EL element are included in the organic transistor. The relationship can be applied to the relationship between the hole injection layer 2 and the organic semiconductor layer 8 in the organic transistor.

In the organic transistor of the present invention, since the hole injection layer 2 is formed on the surfaces of the electrode 1 (source electrode) and the electrode 6 (drain electrode), the molecular order length of the interface between each electrode and the organic semiconductor layer is long. This is preferable from the viewpoint of improving the adhesion stability of the thickness scale (several nm) and contributing to a longer driving life.
The hole injection layer is preferably formed in the same procedure as the hole injection layer of the organic EL element described above.

As a material for forming the organic semiconductor layer, a donor (p-type) low molecular or high molecular organic semiconductor material can be used.
The compound constituting the organic semiconductor layer 8 is a compound represented by the general formula (2), and the hole injection material is a compound represented by the general formula (3). This is preferable from the viewpoint of improving the adhesion stability of the interface of the semiconductor layer and contributing to a longer driving life.

Specifically, it is correct that the organic semiconductor material is TFB represented by the above formula (5), and the hole injection material is TPA-OP (O) Cl ₂ represented by the above formula (6). The interface between the hole injection layer and the hole injection electrode and the interface between the hole injection layer and the organic semiconductor layer can be particularly stabilized to maintain adhesion stability, thereby improving the driving stability and long driving life of the organic transistor. In particular, it contributes greatly.

In addition to the above, as a combination of a donor (p-type) organic semiconductor material and a hole injection material that can be used for the organic transistor of the present invention, when TPA-OP (O) Cl ₂ is used for the hole injection layer Can include arylamine derivatives.
As the organic semiconductor material, materials generally used other than TFB can be used, and porphyrin derivatives, arylamine derivatives, polyacene derivatives, perylene derivatives, rubrene derivatives, coronene derivatives, perylenetetracarboxylic acid diimide derivatives, Perylenetetracarboxylic dianhydride derivatives, polythiophene derivatives, polyparaphenylene derivatives, polyparaphenylene vinylene derivatives, polypyrrole derivatives, polyaniline derivatives, polyfluorene derivatives, polythiophene vinylene derivatives, polythiophene-heterocyclic aromatic copolymers and derivatives thereof, Use α-6-thiophene, α-4-thiophene, naphthalene oligoacene derivatives, α-5-thiophene oligothiophene derivatives, pyromellitic dianhydride derivatives, pyromellitic acid diimide derivatives Rukoto can. Specifically, examples of porphyrin derivatives include metal phthalocyanines such as phthalocyanine and copper phthalocyanine. Examples of arylamine derivatives include m-TDATA. Examples of polyacene derivatives include naphthalene, anthracene, and naphthacene. And pentacene. In addition, a layer having a higher conductivity by mixing such porphyrin derivatives and triphenylamine derivatives with inorganic acids such as Lewis acid, tetracyanoquinodimethane (F ₄ -TCNQ), vanadium and molybdenum. In this case, the mixing ratio is preferably 1 to 95% by weight, but considering the SP value matching, the mixing ratio is 1 to 49%. preferable.
When these materials are used for the organic semiconductor layer, the organic semiconductor compound itself is a low molecular compound, the repeating unit is X for a polymer and a high molecular compound, and Y is the above formula (4). A hole injection material XY having a linking group selected from can be suitably used. For example, when a polythiophene derivative is used as an organic semiconductor material, a hole injection material XY having a thiophene derivative in X part and -OP (O) Cl ₂ or -OSI (OCH ₃ ) ₃ in Y part is used for a hole injection layer. From the viewpoint of matching SP value with SP. Further, when a polyfluorene derivative is used as an organic semiconductor material, for example, as shown in the above formula (10), the X portion has a fluorene derivative and Y is -OP (O) Cl ₂ or -OSI (OCH ₃ ). _It is preferable from the viewpoint of SP value matching to use the material XY with ₃ linked in the hole injection layer.

The carrier mobility of the organic semiconductor layer, which is an organic layer, is preferably 10 ⁻⁶ cm / Vs or more, particularly preferably 10 ⁻³ cm / Vs or more for an organic transistor from the viewpoint of transistor characteristics.
The organic semiconductor layer can be formed by a solution coating method or a dry process, similarly to the light emitting layer of the organic EL element.

The substrate, gate electrode, source electrode, drain electrode, and insulating layer are not particularly limited, and can be formed using the following materials, for example.
The substrate 7 serves as a support for the organic device of the present invention, and may be a flexible material or a hard material, for example. Specifically, the same substrate as that of the organic EL element can be used.
The gate electrode, the source electrode, and the drain electrode are not particularly limited as long as they are conductive materials, but hole injection formed by adsorbing a compound coordinated with metal ions using the charge transport material according to the present invention. From the viewpoint of forming the layer 2, a metal or a metal oxide is preferable. Specifically, the same metal or metal oxide as the electrode in the organic EL element described above can be used, but platinum, gold, silver, copper, aluminum, indium, ITO, and carbon are particularly preferable.

  Various insulating materials can be used for the insulating layer that insulates the gate electrode, and an inorganic oxide or an organic compound can be used. In particular, an inorganic oxide having a high relative dielectric constant is preferable. Inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, Examples thereof include barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, and yttrium trioxide. Of these, silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

  Examples of organic compounds include polyimides, polyamides, polyesters, polyacrylates, photo-curing resins based on radical photopolymerization, photocationic polymerization, or copolymers containing an acrylonitrile component, polyvinylphenol, polyvinyl alcohol, novolac resins, and cyanoethyl. A pullulan, a polymer body, a phosphazene compound including an elastomer body, and the like can be used.

4). Organic Device Manufacturing Method The organic device manufacturing method of the present invention includes two or more electrodes facing a substrate, an organic layer disposed between the two electrodes, and the organic layer side surface of at least one electrode. A hole injection layer adjacent to the electrode, and a method for producing an organic device that may have a metal layer on the electrode,
The compound contained in the organic layer has a part A having a total atomic weight MA of 100 or more as a part of the chemical structure, and the hole injection material contained in the hole injection layer is connected to the electrode. The total MB of the atomic weights and the atomic weight total MB and the total atomic mass MA of the atoms contained in the portion A of the organic layer satisfy the relationship of the following formula (I), In the organic device having the portion B in which the total atomic weight MB is larger than 1/3 of the molecular weight of the hole injection material, the solubility parameter SA of the portion A and the solubility parameter SB of the portion B are expressed by the following formula (II). Meet relationships,
The manufacturing method includes a step of preparing a substrate provided with an electrode;
Applying a solution containing at least the hole injection material having the portion B to form a hole injection layer;
| MA-MB | / MB ≦ 2 Formula (I)
| SA-SB | ≦ 2 Formula (II)
It is characterized by having a step of forming an organic layer by applying a solution containing at least the compound having the portion A on the hole injection layer.

  In the method for producing an organic device according to the present invention, by using a solution coating method, a vapor deposition apparatus is unnecessary when forming the hole injection layer and the organic layer, and the productivity is high. And an organic device having high adhesion stability between the hole injection layer and the organic layer interface.

Here, the solution coating method is a hole injection material or a main material for forming an organic layer (for example, in the case of an organic EL element, it is a hole transport material or a light emitting material, and in the case of an organic transistor, an organic material is used. 1 type or 2 types or more, and if necessary, additives such as a binder resin and a coating property improving agent that do not trap holes are added and dissolved to prepare a coating solution, It is a method of forming a hole injection layer or an organic layer by applying on the hole injection electrode by the above method and drying.
Examples of the solution coating method include a dipping method, a spray coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, and a die coating method. When it is desired to form a monomolecular film, a dipping method or a dip coating method is preferably used.

  A solution for forming a layer by a solution coating method can be prepared by dissolving or dispersing the hole injection material used in the present invention and other components in a solvent. As a solvent used for preparing the solution, a solvent that dissolves the hole injection material according to the present invention is used.

An organic EL device manufacturing method according to an embodiment of an organic device manufacturing method according to the present invention includes a step of forming the organic layer, wherein the organic layer includes a hole transport layer and a light emitting layer, and the hole injection layer. And a step of forming a hole transport layer and a light-emitting layer in this order on the surface.
According to this manufacturing method, when the coating solution containing the hole injection material is applied onto the substrate, the linking group of the hole injection material is selectively connected to the electrode. It is possible to form a hole injection layer that does not contain impurities and has excellent adhesion stability at the interface between the electrode and the hole injection layer and excellent hole injection efficiency.
Further, when the coating solution for forming the hole transport layer is applied onto the hole injection layer, the portion A of the hole injection material and the portion B of the organic layer are selectively connected to each other. Thus, it is possible to form a hole transport layer that is less likely to contain impurities contained in the layer, and has excellent adhesion stability at the interface between the hole injection layer and the hole transport layer, and excellent hole transport characteristics.
Moreover, according to this manufacturing method, a vapor deposition apparatus is unnecessary at the time of formation of a positive hole injection layer and a positive hole transport layer, and an organic EL element can be formed with high productivity.

In the method for manufacturing an organic EL element, the hole transport material constituting the hole transport layer is a compound represented by the general formula (2), and the hole injection material is represented by the general formula (3). A compound is preferable from the viewpoint of further improving the adhesion stability of the interface between the electrode and the hole injection layer and the interface between the hole injection layer and the hole transport layer and contributing to a longer driving life of the organic EL device.
The step of preparing a substrate provided with an electrode and the step of forming a light emitting layer by a solution coating method or a dry process can be performed by a normal method for manufacturing an organic EL element.

Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention. In the examples, parts represent parts by weight unless otherwise specified.
The evaluation methods performed in the examples are as follows.
(1) Measurement of work function The value of the work function (HOMO) described in the present invention was measured using a photoelectron spectrometer AC-1 (manufactured by Riken Keiki Co., Ltd.) unless otherwise specified. Each layer was formed as a single film on a cleaned quartz glass substrate, and the energy value at which photoelectrons were emitted by AC-1 was determined.

(2) Measurement of film thickness Unless otherwise specified, the thickness of each layer described in the present invention was determined by forming each layer as a single film on a cleaned quartz glass substrate and measuring the steps produced. . A probe microscope (manufactured by SII Nanotechnology Inc., Nanopics 1000) was used for film thickness measurement.

(3) Current efficiency and lifetime characteristics of organic EL elements The current efficiency and lifetime characteristics of the organic EL elements fabricated in the examples were evaluated.
The current efficiency was calculated by measuring current-voltage-luminance (IV-L). In the I-V-L measurement method, the cathode was grounded, and a positive DC voltage was applied to the anode by scanning in increments of 50 mV (1 sec./div.), And current and luminance at each voltage were recorded.
The lifetime characteristics were evaluated by observing how the luminance gradually decreased with time by constant current driving. The time until the brightness deteriorates to 50% of the initial brightness was defined as the lifetime.

All the compounds synthesized below were confirmed for their structures by measuring ¹ H NMR spectra using JNM-LA400WB manufactured by JEOL Ltd.
[Synthesis Example 1]
Compound TPA-OP (O) Cl ₂ was synthesized according to the following scheme.

(1) Synthesis of TPA-OH (1) A magnetic stirring bar was placed in a 300 mL three-necked flask equipped with a reflux tube, and argon gas was introduced for 30 minutes to replace the inside of the reaction system. To this was added anhydrous xylene (110 mL), tris-t-butylphosphine (0.43 mL, 1.9 mmol), palladium acetate (0.1 g, 0.48 mmol), sodium t-butoxide (2.2 g, 22.8 mmol). Stir for minutes. Bromobenzene (2.0 mL, 19 mmol) was added to this, and after stirring for 10 minutes, 4-hydroxydiphenylamine (3.1 g, 17 mmol) was added and heated to reflux for 6 hours. After returning to room temperature, chloroform (100 mL) was added, washed with water (200 mL × 1) and saturated brine (200 mL × 1), and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 5.0 g of a pale red solid crude product. This was subjected to flash column chromatography (silica gel 100 g: elution solvent hexane / ethyl acetate = 10/1) to obtain colorless oily TPA-OH (1) (2.8 g, 9.9 mmol; 58% yield). It was.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.20 (t, J = 7.9 Hz, 4H), 7.02 (m, J = 7.6, 8.0 Hz, 6H), 6.93 (t, J = 7.2 Hz, 2H) , 6.77 (d, J = 8.0 Hz, 2H) 5.41 (brs, 1H) ppm.

(2) Synthesis of TPA-OP (O) Cl ₂ (2)
A magnetic stirring bar was placed in a 50 mL three-necked flask, and argon gas was introduced for 30 minutes to replace the inside of the reaction system. TPA-OH (1) (1.5 g, 5.7 mmol) and anhydrous benzene (16 mL) were added to this, and the reaction system was cooled in an ice bath. Phosphoryl chloride (8.4 mL, 90 mmol) was added dropwise, and then a solution of anhydrous pyridine in benzene (1 M, 5.8 mL, 5.8 mmol) was slowly added dropwise. After returning to room temperature and stirring for 2 hours, anhydrous diethyl ether (30 mL) was added, and the precipitated colorless solid was filtered off. The filtrate was concentrated under reduced pressure, and anhydrous diethyl ether (30 mL) was added to the residue. Further, the precipitated colorless solid was removed, and diethyl ether, remaining benzene and phosphoryl chloride in the filtrate were distilled off under reduced pressure to obtain an amorphous solid TPA-OP (O) Cl ₂ (2).
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.27 (m, J = 8.4, 7.9, 7.2 Hz, 4H), 7.13 (dd, J = 9.2, 2.0 Hz, 2H), 7.08 (t, J = 7.2 (Hz, 8H) ppm.

[Synthesis Example 2]
The compound TPA-TPA-OP (O) Cl ₂ was synthesized according to the following scheme.

(1) Synthesis of DPA-OTBDMS (3)
A magnetic stirring bar was placed in a 300 mL three-necked flask, and argon gas was introduced for 30 minutes to replace the inside of the reaction system. To this, anhydrous dichloromethane (110 mL), 4-hydroxydiphenylamine (20 g, 108 mmol), and triethylamine (30 mL, 216 mmol) were added. The reaction system was cooled to 0 ° C., and t-butyldimethylsilane chloride (18 g, 120 mmol) was added over 30 minutes. The mixture was slowly returned to room temperature and stirred for 13 hours. Dichloromethane (200 mL) was added to the resulting brown suspension reaction mixture, washed with water (300 mL × 1) and saturated brine (300 mL × 1), and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 35 g of a pale red solid crude product. This was subjected to flash column chromatography (silica gel 500 g: elution solvent hexane / ethyl acetate = 9/1) to obtain DPA-OTBDMS (3) (31 g, 104 mmol; 96% yield) as a colorless solid. .
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.25 (dd, J = 7.2, 8.8 Hz, 2H), 7.00 (d, J = 8.8 Hz, 2H), 6.91 (d, J = 7.6 Hz, 2H) , 6.83 (t, J = 7.2 Hz, 1H), 6.78 (d, J = 8.8 Hz, 1H), 5.48 (brs, 1H)

(2) Synthesis of TPA-Br-OTBDMS (4) A magnetic stirring bar was placed in a 300 mL three-necked flask equipped with a Dean Stark and a reflux tube, and argon gas was introduced for 30 minutes to replace the inside of the reaction system. DPA-OTBDMS (1) (20 g, 67 mmol), 4-bromo-iodobenzene (19.8 g, 70 mmol), diisopropylbenzene m-, p-isomer mixture (200 mL), copper powder (4.5 g, 72 mmol) and potassium carbonate (20 g, 144 mmol) were added. The reaction system was heated to reflux for 37 hours. After returning to room temperature, the reaction mixture was filtered and washed with dichloromethane (100 mL). The combined filtrate was washed with water (200 mL × 1) and saturated brine (200 mL × 1), and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 25 g of a pale red solid crude product. This was subjected to flash column chromatography (silica gel 700 g: elution solvent hexane / chloroform = 10/1), and light yellow oily TPA-Br-OTBDMS (4) (14.3 g, 22 mmol; 32% yield) Got.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.27 (d, J = 8.8 Hz, 2H), 7.21 (t, J = 8.0 Hz, 2H), 7.02 (d, J = 7.6 Hz, 2H), 6.97 (m, J = 8.8 Hz, 3H), 6.88 (d, J = 8.8 Hz., 2H), 6.76 (d, J = 8.8 Hz, 2H), 0.99 (s, 9H), 0.21 (s, 6H) ppm .

(3) Synthesis of TPA-TPA-OTBDMS (5) A magnetic stirrer was placed in a 250 mL Schlenk type reaction tube equipped with a reflux tube, heated and dried under reduced pressure, and purged with argon gas. TPA-B (OH) ₂ (1.3 g, 4.6 mmol), TPA-Br-OTBDMS (4) (2.0 g, 4.4 mmol), anhydrous toluene (18 mL), distilled water (6 mL), potassium carbonate (3.2 g, 23 mmol) was added, and argon gas replacement under reduced pressure was performed three times for deaeration. Tetrakis (triphenylphosphine) palladium (0) (266 mg, 0.23 mmol) was added to this, and the mixture was heated to reflux at 50 ° C. for 19 hours. The temperature was returned to room temperature, and water (50 mL) and dichloromethane (50 mL) were added. The organic layer was separated, the aqueous layer was extracted with dichloromethane (50 mL × 2), and the combined organic layer was washed with water (100 mL × 1) and saturated brine (100 mL × 1), and anhydrous magnesium sulfate Dried. The solvent was distilled off under reduced pressure to obtain 4.3 g of a reddish brown solid crude product. This was subjected to flash column chromatography (silica gel 50 g: elution solvent hexane / chloroform = 20/1) to obtain TPA-TPA-OTBDMS (5) (1.7 g, 2.7 mmol; 62% yield) as a colorless solid. It was.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.45 (t, J = 3.2 Hz, 2H), 7.41 (d, J = 7.6 Hz, 3H), 7.25 (m, 4H), 7.15 (m, 20H) , 6.77 (d, J = 8.8 Hz, 2H), 0.99 (s, 9H), 0.21 (s, 6H), ppm.

(4) Synthesis of TPA-TPA-OH (6)
A magnetic stir bar was placed in a 50 mL eggplant-shaped flask, and TPA-TPA-OTBDMS (5) (1.7 g, 2.7 mmol) and anhydrous tetrahydrofuran (THF) (10 mL) were added. To this, tetrabutylammonium fluoride 1.0 M THF solution (3.0 mL, 3.0 mmol) was added dropwise and stirred at room temperature for 2 hours. Ethyl acetate (30 mL) was added, washed with water (30 mL × 3) and saturated brine (100 mL × 1), and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 1.8 g of a brown white solid crude product. This was subjected to flash column chromatography (silica gel 30 g: elution solvent hexane / chloroform = 10/1) to obtain colorless solid TPA-TPA-OH (6) (1.0 g, 2.0 mmol; 72% yield). It was.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.42 (brs 5H), 7.25 (m, 8H), 7.11 (m, 10H), 7.01 (t, J = 7.2 Hz, 2H), 6.79 (m, 2H ), 4.68 (brs, 1H), ppm.

(5) Synthesis of TPA-TPA-OP (O) Cl ₂
A magnetic stirring bar was placed in a 50 mL three-necked flask, and argon gas was introduced for 30 minutes to replace the inside of the reaction system. TPA-TPA-OH (6) (1.0 g, 2.0 mmol) and anhydrous benzene (5.6 mL) were added to this and the reaction system was cooled in an ice bath. Phosphoryl chloride (2.9 mL, 31 mmol) was added dropwise, and then a solution of anhydrous pyridine in benzene (1 M, 2.0 mL, 2.0 mmol) was slowly added dropwise. After returning to room temperature and stirring for 2 hours, anhydrous diethyl ether (20 mL) was added, and the precipitated colorless solid was filtered off. The filtrate was concentrated under reduced pressure, and anhydrous diethyl ether (20 mL) was added to the residue. Further, the precipitated colorless solid was removed, and diethyl ether, benzene and phosphoryl chloride in the filtrate were distilled off under reduced pressure to obtain an amorphous solid TPA-TPA-OP (O) Cl ₂ .
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.43 (brs 5H), 7.25 (m, 8H), 7.11 (m, 14H), ppm.
[Synthesis Example 3]
The compound FO-TPA-OP (O) Cl ₂ was synthesized according to the following scheme.

(1) Synthesis of FO-TPA-OTBDMS (8) A magnetic stirring bar was placed in a 250 mL Schlenk type reaction tube equipped with a reflux tube, heated and dried under reduced pressure, and purged with argon gas. FO-B (OH) ₂ (2.0 g, 8 mmol), Br-TPA-OTBDMS (4) (2.0 g, 4.4 mmol), anhydrous toluene (18 mL), distilled water (6 mL), potassium carbonate (3.2 g, 23 mmol) was added, and argon gas replacement under reduced pressure was performed three times for deaeration. Dichlorobistriphenylphosphine palladium (II) dichloromethane complex (161 mg, 0.23 mmol) was added to this, and the mixture was heated and stirred at 50 ° C. for 19 hours. The temperature was returned to room temperature, and water (50 mL) and dichloromethane (50 mL) were added. The organic layer was separated, the aqueous layer was extracted with dichloromethane (50 mL × 2), and the combined organic layer was washed with water (100 mL × 1) and saturated brine (100 mL × 1), and anhydrous magnesium sulfate Dried. The solvent was distilled off under reduced pressure to obtain 4.0 g of a crude product as a reddish brown solid. This was subjected to flash column chromatography (silica gel 100 g: elution solvent hexane / chloroform = 20/1), and FO-TPA-OTBDMS (8) (1.5 g, 1.8 mmol; 95% yield) was obtained as a colorless oil. Obtained.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.70 (t, J = 7.2 Hz, 2H), 7.52 (d, J = 8.0 Hz, 4H), 7.25 (m, 4H), 7.06 (m, 8H) , 6.78 (d, J = 8.8 Hz, 2H), 1.97 (dd, J = 6.8, 9.6 Hz, 4H), 1.10 (m, 20H), 0.99 (s, 9H), 0.80 (t, 7.6 Hz, 6H) , 0.65 (brs, 4H), 0.22 (s, 6H), ppm.

(2) Synthesis of FO-TPA-OH (9)
A magnetic stirring bar was placed in a 50 mL eggplant-shaped flask, and FO-TPA-OTBDMS (8) (1.5 g, 2.0 mmol) and anhydrous THF (9 mL) were added. To this was added dropwise tetrabutylammonium fluoride 1.0 M THF solution (2.0 mL, 2.0 mmol), and the mixture was stirred at room temperature for 2 hours. Ethyl acetate (30 mL) was added, washed with water (30 mL × 3) and saturated brine (100 mL × 1), and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 1.7 g of a brown white solid crude product. This was subjected to flash column chromatography (silica gel 30 g: elution solvent hexane / chloroform = 10/1) to obtain FO-TPA-OH (9) (1.2 g, 2.0 mmol; 72% yield) as a colorless solid. It was.
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.70 (t, J = 7.2 Hz, 2H), 7.52 (br, 4H), 7.33 (m, 4H), 7.06 (m, 8H), 6.78 (br, 2H), 1.97 (dd, J = 6.0, 9.6 Hz, 4H), 1.10 (m, 20H), 0.80 (t, 7.6 Hz, 6H), 0.65 (brs, 4H), ppm.

(3) Synthesis of FO-TPA-OP (O) Cl ₂
A magnetic stirring bar was placed in a 50 mL three-necked flask, and argon gas was introduced for 30 minutes to replace the inside of the reaction system. FO-TPA-OH (9) (1.2 g, 2.0 mmol) and anhydrous benzene (5.1 mL) were added to this, and the reaction system was cooled in an ice bath. Phosphoryl chloride (2.7 mL, 29 mmol) was added dropwise, and then a solution of anhydrous pyridine in benzene (1 M, 1.9 mL, 1.9 mmol) was slowly added dropwise. After returning to room temperature and stirring for 2 hours, anhydrous diethyl ether (20 mL) was added, and the precipitated colorless solid was filtered off. The filtrate was concentrated under reduced pressure, and anhydrous diethyl ether (20 mL) was added to the residue. Further, the precipitated colorless solid was removed, and diethyl ether, benzene and phosphoryl chloride in the filtrate were distilled off under reduced pressure to obtain an oily FO-TPA-OP (O) Cl ₂ .
¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.73 (m, J = 7.6, 6.4 Hz, 2H), 7.56 (br, 4H), 7.33 (m, 4H), 7.13 (m, 10H), 1.97 ( dd, J = 7.6, 8.8 Hz, 4H), 1.13 (m, 20H), 0.80 (t, 7.2 Hz, 6H), 0.65 (brs, 4H), ppm.

[Example 1]
On the glass substrate, a transparent anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and a cathode were formed and laminated in this order, and finally sealed to prepare an organic EL device. Except for the transparent anode and the hole injection layer, the work was performed in a nitrogen-substituted glove box having a water concentration of 0.1 ppm or less and an oxygen concentration of 0.1 ppm or less.
First, an indium tin oxide (ITO) thin film (thickness: 150 nm) was used as a transparent anode. A glass substrate with ITO (manufactured by Sanyo Vacuum Co., Ltd.) was patterned into a strip shape. The patterned ITO substrate was ultrasonically cleaned in order of neutral detergent and ultrapure water, and then subjected to UV ozone treatment. The HOMO of ITO after UV ozone treatment was 5.0 eV.
Next, a TPA-OP (O) Cl ₂ film was formed as a hole injection layer on the cleaned anode. For the TPA-OP (O) Cl ₂ film, the anode was immersed for 10 minutes in a solution in which 1 wt% of TPA-OP (O) Cl ₂ obtained in Synthesis Example 1 was dissolved in 1,2-dichloroethane solvent. Thereafter, it was washed with an acetone solution and dried with dry nitrogen. The thickness of the produced thin film was 5 nm or less, which is below the measurement limit, and the work function was 5.3 eV.

Next, poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4 ′-(N- (4 -Sec-butylphenyl)) diphenylamine)] (TFB) thin film (thickness: 20 nm, work function: 5.4 eV). This TFB was manufactured by American Die Source, product number: ADS259BE (molecular weight distribution: 50,000 to 100,000) as a material. A solution in which TFB was dissolved in xylene was applied by spin coating in a glove box to form a film. After forming the TFB film, it was dried using a hot plate in a glove box in order to evaporate xylene.
Next, a tris (8-quinolinolato) aluminum complex (Alq3) thin film (thickness: 60 nm) was formed as a light emitting layer on the prepared hole transport layer. In vacuum (pressure: 1 × 10 ⁻⁴ Pa), a film was formed by resistance heating vapor deposition.

Next, on the produced electron transport layer, LiF (thickness: 0.5 nm) as an electron injection layer and Al (thickness: 150 nm) as a cathode were sequentially formed. In vacuum (pressure: 1 × 10 ⁻⁴ Pa), a film was formed by resistance heating vapor deposition.
Finally, after forming the cathode, sealing was carried out in the glove box using non-alkali glass and a UV curable epoxy adhesive to produce the organic EL device of Example 1.

[Example 2]
Example except that TPA-TPA-OP (O) Cl ₂ obtained in Synthesis Example 2 was used in place of TPA-OP (O) Cl ₂ as a material used for forming the hole injection layer. As in Example 1, the organic EL device of Example 2 was produced.

[Example 3]
Example except that FO-TPA-OP (O) Cl ₂ obtained in Synthesis Example 3 was used in place of TPA-OP (O) Cl ₂ as a material used for forming the hole injection layer. As in Example 1, an organic EL device of Example 3 was produced.

[Comparative Example 1]
In Example 1, instead of TPA-OP (O) Cl ₂ , the hole injection layer was a poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT-PSS) thin film (thickness: 20 nm, manufactured by Starck) An organic EL device was prepared in the same manner as in Example 1 except that the product number was CH 8000, the PEDOT: PSS weight ratio was 1:20, and the work function was 5.3 eV. The PEDOT-PSS thin film was produced by applying a PEDOT-PSS aqueous solution in the air by a spin coating method. After the PEDOT-PSS film formation, the film was dried in the air using a hot plate in order to evaporate water.

[Comparative Example 2]
An organic EL device was produced in the same manner as in Example 1 except that in Example 1, the hole injection layer was produced using Ph-OP (O) Cl ₂ instead of TPA-OP (O) Cl ₂ . The Ph-OP (O) Cl ₂ film is immersed for 10 minutes in a solution of 1% by weight Ph-OP (O) Cl ₂ dissolved in 1,2-dichloroethane solvent, then washed with acetone solution and dried nitrogen And dried. The thickness of the produced thin film was 5 nm or less, which is below the measurement limit, and the work function was 5.3 eV.

[Comparative Example 3]
In Example 1, an organic EL element was produced in the same manner as in Example 1 except that the hole injection layer was not formed.
[Comparative Example 4]
In Example 1, an organic EL device was produced in the same manner as in Example 1 except that the hole transport layer was not formed.

About the organic EL element produced in the said Example and comparative example, the current efficiency and lifetime characteristic were performed by the said method. Initial luminance 1000 (cd / ^{m 2)} Current efficiency of (cd / A), and the initial luminance (1000 cd / ^{m 2)} luminance half-life in the (hr.) Shown in Table 2. In addition, Table 3 shows characteristic values related to the hole transport material and the hole injection material used in Examples and Comparative Examples. Note that Comparative Example 3 and Comparative Example 4 are not shown because the part A and the part B according to the present invention cannot be specified.

<Summary of results>
Comparing the device characteristics of Example 1 and Comparative Example 1, the device using TPA-OP (O) Cl ₂ that has an adhesion effect on both the hole transport layer and the anode is generally used. The lifetime was 6 times longer than the device using PEDOT as the hole injection layer.

PEDOT: PSS (1:20) used for the hole injection layer of the device of Comparative Example 1 tends to have a higher SP value than TFB, for example, SP of PEDOT (total of atomic weights of repeating units: 72). The SP value (SB) of PEDOT: PSS (1:20) consisting of the value 21.7 and the SP value 24.4 of PSS (sum of the atomic weights of repeating units: 104) depends on the mixed state. It is considered to be in the range of 7 to 24.4. On the other hand, the SP value (SA) of the corresponding repeated partial TPA-FO (triphenylamine-fluorene) (total atomic weight of repeating units: 634) in TFB is 19.1, and | SA-SB | It becomes a large value of 6 to 5.3. For this reason, it is considered that the compatibility at the interface between the hole transport layer and the hole transport layer is poor, the adhesion stability at the molecular size (length scale adhesion stability on the order of nm) is inferior, and the lifetime of the device is short. PEDOT: PSS (1:20) is a polymer, and the film thickness is relatively thick. PSS sulfonic acid groups and PEDOT: PSS are randomly exposed at the air interface after the hole injection layer is formed. Part 3 to be compared is as shown in Table 3.
On the other hand, since the element of Example 1 using TPA-OP (O) Cl ₂ for the hole injection layer satisfies all the conditions of the organic EL element according to the present invention, the adhesion stability of the interface between each layer is excellent. It is considered that the driving tolerance was improved.

Comparing the device characteristics of Example 1 and Comparative Example 2, the device using Ph-OP (O) Cl ₂ as the hole injection material has an extremely longer lifetime than the device using TPA-OP (O) Cl _2. Was short.
Of _{Ph-OP (O) Cl 2} , portions considered to have an effect on adhesion stability of the interface between the TFB and Ph-OP (O) Cl ₂ is a phenyl group, TFB corresponding to the portion In the molecule is a (9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4 ′-(N- (4-sec-butylphenyl) ( Although the phenyl group has a total atomic weight of less than 100, it is not suitable as the part B according to the present invention, but the phenyl group of Ph-OP (O) Cl ₂ is represented by the part B, TPA- When FO is regarded as the part A, the relational expression (II) according to the present invention is satisfied, but since the total MA of the atomic weights of the part A is less than 100, TFB and Ph-OP (O) Cl ₂ It is considered that the adhesion stability at the interface with the substrate was insufficient, and the device life was extremely short.

Comparing the device characteristics of Example 1 and Comparative Example 3, in Comparative Example 3 without TPA-OP (O) Cl ₂ , the efficiency in the initial characteristics was high, but the lifetime was extremely short. Even without TPA-OP (O) Cl ₂ , holes can be sufficiently injected with TFB alone, but the adhesion stability between the inorganic anode (ITO) and TFB is poor, and it is considered that the driving durability is remarkably inferior. From the above results, it can be seen that there is no correlation among charge injection properties, efficiency, and lifetime, and it can be seen that the effect is different from that of Patent Document 2.

When the life characteristics of Example 1 and Comparative Example 4 were compared, Comparative Example 4 without TFB showed a significantly lower efficiency than the initial characteristics. This result indicates that hole injection is insufficient with only TPA-OP (O) Cl ₂ , and that the injection effect can be obtained by the effect of the dipole moment (Japanese Patent Laid-Open No. 2005-50553). (Publication) cannot explain. Furthermore, TPA-OP (O) Cl ₂ is considered to have a very small dipole moment due to its chemical structure, and TPA-OP (O) Cl ₂ contributes to the adhesion stability between the hole transport layer and the anode and has life characteristics. It is thought that it is improving.
The above results indicate that TPA-OP (O) Cl ₂ has the effect of improving not only the effect of hole injection but also the adhesion stability between the hole transport layer and the anode and the life characteristics.

  When the device characteristics of Example 1 and Example 2 are compared, the luminance half time of Example 2 is slightly longer. From this result, it is considered that Example 2 in which the molecular weight of the portion B is larger has higher adhesion to the hole transport layer, and the lifetime is improved by improving the adhesion stability.

  Comparing the device characteristics of Example 1 and Example 3, the luminance half time of Example 3 is 1.5 times longer. As a result, it is considered that Example 3 having the portion B having higher compatibility with the hole transport layer material has higher adhesion with the hole transport layer, and the lifetime is improved by improving the adhesion stability. It is done.

It is a section conceptual diagram showing the basic layer composition of the organic device concerning the present invention. It is a cross-sectional schematic diagram which shows an example of the laminated constitution of the organic EL element which is one Embodiment of the organic device which concerns on this invention. It is a cross-sectional schematic diagram which shows an example of the layer structure of the organic transistor which is another embodiment of the organic device which concerns on this invention. It is a section conceptual diagram of a layered product in which an organic layer is laminated on an electrode made of an inorganic material and there is a difference in SP value between both materials forming an interface.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrode 2 Hole injection layer 3 Organic layer 4 Hole transport layer 5 Light emitting layer 6 Electrode 7 Substrate 8 Organic semiconductor layer 9 Electrode 10 Insulating layer

Claims (16)

Two or more electrodes facing on the substrate, an organic layer disposed between the two electrodes, and a hole injection layer adjacent to the organic layer side surface of at least one electrode, An organic device that may have a metal layer on the electrode,
The compound contained in the organic layer has, as part of its chemical structure, a portion A having a total atomic mass MA of 100 or more,
The hole injection material contained in the hole injection layer has, as part of its chemical structure, a linking group that has an effect of linking with the electrode on which the hole injection material is laminated, and the total atomic weight MB is 100 or more. The sum MB of the atomic weights and the sum MA of the atomic weights of the atoms contained in the portion A of the organic layer satisfy the relationship of the following formula (I), and the sum MB of the atomic weights is 1 / of the molecular weight of the hole injection material. Having a portion B greater than 3;
An organic device, wherein the solubility parameter SA of the part A and the solubility parameter SB of the part B satisfy the relationship of the following formula (II).
| MA-MB | / MB ≦ 2 Formula (I)
| SA-SB | ≦ 2 Formula (II) The organic device according to claim 1, wherein the hole injection layer contains a hole injection material represented by the following general formula (1).
XY (1)
However, X is a part including the part B and ensuring adhesion stability with the organic layer. Y is a connecting group connected to the electrode.   The organic device according to claim 1, wherein the portion B has the same skeleton as the portion A or a similar skeleton including a spacer structure in the same skeleton.   When the hole injection material is a compound represented by the general formula (1), the total atomic weight MB of atoms contained in the portion B is larger than 1/3 of the total atomic weight of atoms contained in X. The organic device according to claim 2, characterized in that:   The organic device according to claim 1, wherein the hole injection layer has a thickness of 0.1 to 1000 nm.   The organic device according to claim 1, wherein a work function of the hole injection layer is 4.5 to 6.0 eV.   The organic device according to claim 1, wherein the hole injection layer is formed by a solution coating method.   The organic device according to claim 1, wherein the organic layer is formed on the hole injection layer by a solution coating method.   The organic device according to claim 1, wherein the organic layer of the organic device is an organic EL element including at least a hole transport layer and a light emitting layer. The hole transport material contained in the hole transport layer is a compound represented by the following general formula (2), and the hole injection material is a compound represented by the following general formula (3). Organic devices.

(However, Ar _{1 to} Ar ₄ may be the same as or different from each other, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 60 carbon atoms related to the conjugated bond, or An unsubstituted or substituted heterocyclic group having 4 or more and 60 or less carbon atoms related to a conjugated bond is shown, n is 0 to 10,000, m is 0 to 10,000, and n + m = 1 to 20,000. The arrangement of the two repeating units is arbitrary.)

(However, Ar _{5 to} Ar ₇ may be the same as or different from each other, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 60 carbon atoms related to the conjugated bond, or An unsubstituted or substituted heterocyclic group having 4 to 60 carbon atoms with respect to a conjugated bond is shown.) Two or more electrodes facing on the substrate, an organic layer disposed between the two electrodes, and a hole injection layer adjacent to the surface of the at least one electrode on the organic layer side, A method for producing an organic device that may have a metal layer on an electrode,
The compound contained in the organic layer has a part A having a total atomic weight MA of 100 or more as a part of the chemical structure, and the hole injection material contained in the hole injection layer is connected to the electrode. The total MB of the atomic weights and the atomic weight total MB and the total atomic mass MA of the atoms contained in the portion A of the organic layer satisfy the relationship of the following formula (I), In the organic device having the portion B in which the total atomic weight MB is larger than 1/3 of the molecular weight of the hole injection material, the solubility parameter SA of the portion A and the solubility parameter SB of the portion B are expressed by the following formula (II). Meet relationships,
| MA-MB | / MB ≦ 2 Formula (I)
| SA-SB | ≦ 2 Formula (II)
The manufacturing method includes a step of preparing a substrate provided with an electrode;
Applying a solution containing at least the hole injection material having the portion B to form a hole injection layer;
A method for producing an organic device, comprising: applying a solution containing at least the compound having the part A onto the hole injection layer to form an organic layer. The method for producing an organic device according to claim 11, wherein the hole injection layer contains a hole injection material represented by the following general formula (1).
XY (1)
However, X includes the portion B. Y is a connecting group connected to the electrode.   The method for manufacturing an organic device according to claim 11, wherein the portion B has the same skeleton as the portion A or a similar skeleton including a spacer structure in the same skeleton.   When the hole injection material is a compound represented by the general formula (1), the total atomic weight MB of atoms contained in the portion B is larger than 1/3 of the total atomic weight of atoms contained in the X. The method for producing an organic device according to claim 12, wherein the organic device is produced. In the step of forming the organic layer of the organic device manufacturing method according to claim 11 to 14, the organic layer includes a hole transport layer and a light emitting layer,
The manufacturing method of the organic device in any one of Claims 11 thru | or 14 which is a manufacturing method of the organic EL element which has the process of forming in order of a positive hole transport layer and a light emitting layer on the surface of the said positive hole injection layer. The hole transport material contained in the hole transport layer is a compound represented by the following general formula (2), and the hole injection material is a compound represented by the following general formula (3). Manufacturing method of organic device.

(However, Ar _{1 to} Ar ₄ may be the same as or different from each other, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 60 carbon atoms related to the conjugated bond, or An unsubstituted or substituted heterocyclic group having 4 or more and 60 or less carbon atoms related to a conjugated bond is shown, n is 0 to 10,000, m is 0 to 10,000, and n + m = 1 to 20,000. The arrangement of the two repeating units is arbitrary.)

(However, Ar _{5 to} Ar ₇ may be the same as or different from each other, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 60 carbon atoms related to the conjugated bond, or An unsubstituted or substituted heterocyclic group having 4 to 60 carbon atoms with respect to a conjugated bond is shown.)

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