JP2010034085A - Organic electroluminescent device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent device that reduces damage on an organic electroluminescent layer in forming an electrode layer, and can display a high-quality image. <P>SOLUTION: The organic electroluminescent device includes a base material, a first electrode layer formed on the base material, the organic electroluminescent layer formed on the first electrode layer and having at least a light emitting layer, a semiconductor buffer layer formed on the organic electroluminescent layer and containing an inorganic compound and metal of which band gaps are 2.0 eV or more, and a second electrode layer formed on the semiconductor buffer layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic electroluminescence (hereinafter sometimes abbreviated as organic EL) element.

  Organic EL elements have high visibility due to self-coloring, are all solid-state displays unlike liquid crystal displays, have excellent impact resistance, have a fast response speed, are less affected by temperature changes, and have a field of view. It has advantages such as a large angle, and its use as a light-emitting element in an image display device has attracted attention.

  The structure of the organic EL element is based on a laminated structure of anode / light emitting layer / cathode, and a structure in which an anode that is a transparent electrode is formed on a substrate such as a glass substrate is usually employed. In this case, light emission is taken out from the substrate side (anode side).

  On the other hand, in recent years, attempts have been made to extract light emission from the cathode side using the cathode as a transparent electrode, that is, to emit light from the top surface. By realizing the top emission, when the anode as well as the cathode is a transparent electrode, it becomes possible to obtain a transparent light emitting element as a whole, and double-sided emission can be realized. Such a transparent light-emitting element can employ any color as a background color, so that it is possible to obtain a colored display even when light is not emitted, and the decorativeness is improved. In addition, when a color filter layer or a color conversion layer is formed on a light emitting element, a color filter layer or a color conversion layer is formed on the light emitting layer even in a light emitting element capable of emitting light on the top surface in the same manner as a conventional bottom emitting light emitting element. They can be placed together. Further, in a light-emitting element capable of top emission, light emission is not blocked by a TFT (thin film transistor) of an active drive display device, and thus a display device with a high aperture ratio can be obtained.

  As an example of an organic EL device that can emit light from the top surface by using a transparent electrode as a cathode, Patent Document 1 discloses that an organic EL layer including a light emitting layer is interposed between an anode and a cathode, and the cathode is an electron injection layer. An organic EL element is disclosed which is composed of a transparent electrode layer and is disposed so that the electron injection layer is in contact with the organic EL layer.

However, in a conventional organic EL device capable of top emission or double-side emission, a transparent electrode such as ITO is generally formed by sputtering, and an organic layer including a light emitting layer is formed when forming the transparent electrode. Under the impact of EL layer, particles with electron injection layer or hole injection layer sputtered, Ar ⁺ during sputtering, ionized electrons, etc., the emission characteristics are reduced (current density is reduced, emission efficiency is reduced, There is a problem that a leakage current occurs. Furthermore, when forming a cathode that is a transparent electrode, the highly reactive metal contained in the electron injection layer is oxidized due to the introduction of oxygen or the release of oxygen from the target. There has also been a problem of causing characteristic deterioration (decrease in current density characteristics, reduction in light emission efficiency, increase in dark spots). If there is such a problem, a high-quality image display cannot be obtained.

  Therefore, an attempt to form a buffer layer, a barrier layer, or the like between the cathode and the organic EL layer in order to improve the deterioration of the light emission characteristics or the deterioration of the characteristics of the organic EL layer or the electron injection layer due to impact during the cathode film formation. Has been made. For example, Patent Document 2 discloses an organic EL element using CuPc as a buffer layer for the purpose of preventing damage to the organic EL layer due to sputtering when forming a cathode. In Patent Document 3, a Ca diffusion barrier layer is provided between the cathode and the organic EL layer in order to prevent the constituent material of the cathode from diffusing into the organic EL layer including the light emitting layer. A method for preventing a short circuit and deterioration of characteristics is disclosed. Further, Patent Document 4 and Patent Document 5 disclose an organic EL element in which a semiconductor such as ZnSe, ZnS, or CdS is interposed between a cathode and an organic EL layer in order to improve electron transport from the cathode. Has been. Patent Document 6 discloses an organic EL element in which a conductor layer such as Ag, Mg, or TiN is interposed between a cathode and an organic EL layer including a light emitting layer in order to reduce the resistance of the cathode. ing.

  However, when a buffer layer, a barrier layer, or the like (organic matter, semiconductor, etc.) as described above is inserted, the organic EL element (organic EL element using a conductive polymer) that is driven under a high current density is used. There is a problem that current density-voltage characteristics are deteriorated as compared with an organic EL device that extracts light emission from the device.

Japanese Patent Laid-Open No. 10-162959 JP 2002-75658 A Japanese Patent Laid-Open No. 10-144957 JP-A-10-223377 JP 2000-215984 A JP-A-10-125469

  The present invention has been made in view of the above problems, and provides an organic EL element capable of reducing damage to an organic EL layer when forming an electrode layer and capable of displaying a high-quality image. This is the main purpose.

  In order to achieve the above object, the present invention provides a base material, a first electrode layer formed on the base material, an organic EL layer formed on the first electrode layer and having at least a light emitting layer. A semiconductor buffer layer formed on the organic EL layer and containing an inorganic compound and a metal having a band gap of 2.0 eV or more, and a second electrode layer formed on the semiconductor buffer layer. An organic EL element is provided.

  According to the present invention, since the semiconductor buffer layer is formed between the organic EL layer and the second electrode layer, the sputtered particles at the time of forming the second electrode layer, the plasma gas ions at the time of sputtering, and Impact due to ionized electrons can be alleviated, and deterioration of the characteristics of the organic EL layer and emission characteristics of the organic EL element can be prevented. Moreover, since the semiconductor buffer layer contains an inorganic compound and a metal, and the electrical resistivity of this metal is lower than that of the inorganic compound, it is possible to prevent a decrease in current density-voltage characteristics. As a result, an organic EL element capable of displaying a high-quality image can be obtained.

  The present invention is also formed on a base material, an electrode layer formed on the base material, an organic EL layer formed on the electrode layer and having at least a light emitting layer, and the organic EL layer, Provided is an organic EL element comprising an inorganic compound having a band gap of 2.0 eV or more and a semiconductor electrode layer containing a metal.

  According to the present invention, since the semiconductor electrode layer is formed by, for example, a vacuum deposition method, the organic EL layer is not shocked when the semiconductor electrode layer is formed, and the deterioration of the light emission characteristics of the organic EL element is avoided. can do. In addition, since oxygen is not normally introduced in the vacuum deposition method, for example, even when an electron injection layer is formed between the light emitting layer and the semiconductor electrode layer, the metal contained in this electron injection layer The oxidation of can be avoided.

  In the present invention, the semiconductor buffer layer or the semiconductor electrode layer may be a mixed semiconductor layer in which the metal is dispersed in the inorganic compound.

  Furthermore, in the present invention, the semiconductor buffer layer has an inorganic layer made of the inorganic compound and a metal layer made of the metal, and the metal layer is in the inorganic layer or the inorganic layer and the second electrode. It may be formed between the layers. On the other hand, the semiconductor electrode layer has an inorganic layer made of the inorganic compound and a metal layer made of the metal, and the metal layer is opposite to the surface in the inorganic layer or the surface on which the organic EL layer is formed. It may be formed on the surface.

  In the present invention, the semiconductor buffer layer or the semiconductor electrode layer may have a mixed semiconductor layer in which the metal is dispersed in the inorganic compound and an inorganic layer made of the inorganic compound. The semiconductor buffer layer or the semiconductor electrode layer may include a mixed semiconductor layer in which the metal is dispersed in the inorganic compound and a metal layer made of the metal.

Furthermore, in the present invention, the electrical resistivity ρ of the metal is preferably less than 1 × 10 ⁻⁵ Ω · cm. This is because the electrical conductivity of the semiconductor buffer layer or the semiconductor electrode layer can be increased when the electrical resistivity of the metal is within the above range.

  In the present invention, the work function of the metal contained in the semiconductor electrode layer is preferably 4.2 eV or more.

  Furthermore, in the present invention, the inorganic compound may be an inorganic semiconductor compound. In this case, the inorganic semiconductor compound is preferably a compound containing at least one element selected from elements from Group 12 to Group 16 of the Group 18 element periodic table. This is because such a compound has a large band gap and is transparent.

  In the present invention, the inorganic compound may be a metal compound containing at least one element selected from Group 17 elements of the Group 18 element periodic table.

  Further, in the present invention, the semiconductor buffer layer or the semiconductor electrode layer preferably has a thickness in the range of 1 nm to 500 nm and an average light transmittance in the visible region of 30% or more. This is because if the thickness of the semiconductor buffer layer or the semiconductor electrode layer is too thick, the light transmittance may be lowered. Conversely, if the thickness of the semiconductor buffer layer is too thin, there is a possibility that the effect of protecting the organic EL layer from impact during film formation of the second electrode layer may not be obtained, and the thickness of the semiconductor electrode layer is thin. This is because if it is too large, it may not function as an electrode.

  Moreover, in this invention, it is preferable that content of the said metal in the said semiconductor buffer layer or the said semiconductor electrode layer exists in the range of 0.0001 volume%-90 volume%. This is because if the content of the metal is too large, the light transmittance of the semiconductor buffer layer or the semiconductor electrode layer may be lowered. Conversely, if the content of the metal is too small, the effect of increasing the electrical conductivity of the semiconductor buffer layer or the semiconductor electrode layer may not be obtained.

  Furthermore, in the present invention, when the metal contained in the semiconductor buffer layer or the semiconductor electrode layer is a layer made of only a metal, the thickness of the layer made of only the metal is 100 nm or less. Further, it is preferably contained in the semiconductor buffer layer or the semiconductor electrode layer. It is because the light transmittance of a semiconductor buffer layer or a semiconductor electrode layer may fall when the thickness of the layer which consists only of the said metal is too thick.

  In the present invention, the semiconductor buffer layer or the semiconductor electrode layer is preferably formed by a vacuum deposition method. In the vacuum deposition method, since oxygen is not usually introduced, for example, even when an electron injection layer is formed between the light emitting layer and the semiconductor buffer layer or the semiconductor electrode layer, it is contained in this electron injection layer. This is because oxidation of the metal to be performed can be avoided.

  Furthermore, in the present invention, a charge injection / transport layer may be formed between the light emitting layer and the semiconductor buffer layer or the semiconductor electrode layer. This is because charge injection into the light emitting layer is stabilized and the light emission efficiency can be increased.

  In the present invention, since the semiconductor buffer layer is formed between the organic EL layer and the second electrode layer, damage to the organic EL layer due to impact at the time of forming the second electrode layer can be mitigated. For example, even when an electron injection layer is formed between the light emitting layer and the semiconductor buffer layer, oxidation of the metal contained in the electron injection layer can be prevented. From the above, in the present invention, there is an effect that it is possible to suppress deterioration in characteristics of the organic EL layer and emission characteristics of the organic EL element.

It is a schematic sectional drawing which shows an example of the organic EL element of this invention. It is a schematic sectional drawing which shows the other example of the organic EL element of this invention. It is a schematic sectional drawing which shows the other example of the organic EL element of this invention. It is a schematic sectional drawing which shows the other example of the organic EL element of this invention. It is a schematic sectional drawing which shows the other example of the organic EL element of this invention. It is a schematic sectional drawing which shows the other example of the organic EL element of this invention. It is a schematic sectional drawing which shows the other example of the organic EL element of this invention. It is a schematic sectional drawing which shows the other example of the organic EL element of this invention.

Hereinafter, the organic EL device of the present invention will be described in detail.
The organic EL device of the present invention can be divided into two embodiments depending on the configuration of the organic EL device. A first embodiment of the organic EL element of the present invention includes a base material, a first electrode layer formed on the base material, an organic EL layer formed on the first electrode layer and having at least a light emitting layer. And a semiconductor buffer layer containing an inorganic compound and a metal formed on the organic EL layer and having a band gap of 2.0 eV or more, and a second electrode layer formed on the semiconductor buffer layer. It is a feature. Further, the second embodiment of the organic EL element of the present invention is a substrate, an electrode layer formed on the substrate, an organic EL layer formed on the electrode layer and having at least a light emitting layer, It has a semiconductor electrode layer formed on the organic EL layer and containing a metal and an inorganic compound having a band gap of 2.0 eV or more. Each embodiment will be described below.

1. First Embodiment A first embodiment of the organic EL device of the present invention includes a base material, a first electrode layer formed on the base material, and a light emitting layer formed on the first electrode layer. An organic EL layer, a semiconductor buffer layer formed on the organic EL layer and containing an inorganic compound and a metal having a band gap of 2.0 eV or more, and a second electrode layer formed on the semiconductor buffer layer, It is characterized by having.

  The organic EL element of this embodiment will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the organic EL element of this embodiment. In FIG. 1, an organic EL element includes a base material 1, a first electrode layer 2 formed on the base material 1, and an organic EL layer 3 formed on the first electrode layer 2 and having at least a light emitting layer. An electron injection layer 6 formed on the organic EL layer 3, a semiconductor buffer layer 4 formed on the electron injection layer 6, and a second electrode layer 5 formed on the semiconductor buffer layer 4. have.

Conventionally, for example, when the electrode layer is deposited on the organic EL layer by sputtering, a few hundred volts with a high amount of energy Ar ^+, since the organic EL layer is subjected to impact due to sputtered particles and ionized electrons and the like, organic The structure of the EL layer has changed, and there has been a problem that non-radiative quenching is caused at the interface between the organic EL layer and the electrode layer in charge injection, resulting in a decrease in light emission characteristics. For example, when an electron injection layer containing an alkali metal or an alkaline earth metal is formed between the light emitting layer and the semiconductor buffer layer, these metals are easily oxidized. There is a possibility that the above metal is oxidized by introducing oxygen or releasing oxygen from the target, and the charge injection function is lost. On the other hand, in this embodiment, since the semiconductor buffer layer is formed between the organic EL layer and the second electrode layer, even when the second electrode layer is formed by sputtering, Since the impact on the organic EL layer due to plasma gas ions, sputtered particles, ionized electrons, and the like can be mitigated, it is possible to prevent deterioration of the characteristics of the organic EL layer and the emission characteristics of the organic EL element. Further, for example, when an electron injection layer is formed between the light emitting layer and the semiconductor buffer layer, the electron injection layer is protected by the semiconductor buffer layer, so that oxidation of the metal contained in the electron injection layer is prevented. can do. Thereby, the luminous efficiency and durability of the organic EL element can be improved, and an organic EL element capable of displaying a high-quality image can be obtained.

In addition, since an inorganic compound generally has a low electrical resistivity, when a layer made of only an inorganic compound is formed between the organic EL layer and the second electrode layer, the current density under a high voltage (high current density region) is high. There is a problem that the luminance does not increase and the luminance does not improve. On the other hand, the semiconductor buffer layer used in the present embodiment contains an inorganic compound and a metal, and since the electrical resistivity of this metal is lower than that of the inorganic compound, the current density-voltage characteristic is prevented from being lowered. can do. Thereby, it can use suitably for the organic EL element (organic EL element using an electroconductive polymer) driven under high current density, for example.
Hereinafter, each structure of such an organic EL element is demonstrated.

(1) Semiconductor Buffer Layer First, the semiconductor buffer layer used in this embodiment will be described. The semiconductor buffer layer used in this embodiment is formed between the organic EL layer and the second electrode layer and contains an inorganic compound and a metal having a band gap of 2.0 eV or more.

  As described above, the semiconductor buffer layer in the present embodiment has two functions: a function of protecting the organic EL layer when the second electrode layer is formed, and a function of transporting and injecting charges into the organic EL layer. It is. When a charge injection / transport layer is formed between the semiconductor buffer layer and the light emitting layer, the semiconductor buffer layer protects the charge injection / transport layer, and transports / injects charge into the charge injection / transport layer. It also has a function to perform. In this embodiment, by forming a semiconductor buffer layer between the organic EL layer and the second electrode layer, it is possible to mitigate the impact when the second electrode layer is formed on the organic EL layer. Moreover, when the electron injection layer is formed between the light emitting layer and the semiconductor buffer layer, the oxidation of the metal contained in this electron injection layer can be prevented. Furthermore, when the semiconductor buffer layer contains a metal, it is possible to suppress a decrease in current density-voltage characteristics. Thereby, the luminous efficiency and durability of the organic EL element can be improved.

The semiconductor buffer layer used in this embodiment can be divided into four modes depending on the configuration of the semiconductor buffer layer. That is, when the semiconductor buffer layer is a mixed semiconductor layer in which a metal is dispersed in an inorganic compound (first aspect), the semiconductor buffer layer includes an inorganic layer made of an inorganic compound and a metal layer made of a metal. In the case where the metal layer is formed in the inorganic layer or between the inorganic layer and the second electrode layer (second embodiment), the semiconductor buffer layer has a metal dispersed in the inorganic compound. When the mixed semiconductor layer has an inorganic layer made of an inorganic compound (third embodiment), and the semiconductor buffer layer includes a mixed semiconductor layer in which a metal is dispersed in an inorganic compound and a metal layer made of a metal (4th aspect).
Hereinafter, each aspect of such a semiconductor buffer layer will be described.

(I) 1st aspect The 1st aspect of the semiconductor buffer layer used for this embodiment is a mixed semiconductor layer by which the metal was disperse | distributed in the inorganic compound. In this aspect, since the metal is dispersed in the mixed semiconductor layer, the electrical resistivity of the mixed semiconductor layer can be lowered, and a decrease in current density-voltage characteristics can be suppressed.
Hereinafter, constituent materials of such a mixed semiconductor layer will be described.

(Inorganic compounds)
The inorganic compound used in this embodiment has a band gap of 2.0 eV or more. The inorganic compound used in this embodiment can be a layer having a protective function that reduces the impact on the organic EL layer or the charge injecting and transporting layer when the second electrode layer is formed as described above. If it is, it will not specifically limit. The band gap of the inorganic compound may be 2.0 eV or more, preferably 2.4 eV or more, and particularly preferably 2.6 eV or more. This is because when the band gap of the inorganic compound is in the above range, the light transmittance in the visible region of the mixed semiconductor layer can be increased. In addition, if the band gap is too small, the mixed semiconductor layer may be colored, which may reduce the light transmittance in the visible region. On the other hand, the upper limit of the band gap of the inorganic compound is not particularly limited because the light transmission increases as the band gap increases, but it is usually set to 30 eV or less.

  As such an inorganic compound, an inorganic semiconductor compound having a predetermined band gap or an insulating compound having optical transparency can be given. In this embodiment, it is particularly preferable to use an inorganic semiconductor compound.

  As described above, the inorganic semiconductor compound may be a layer having a protective function that reduces the impact on the organic EL layer or the charge injecting and transporting layer when the second electrode layer is formed. There is no particular limitation. In addition, the band gap of the inorganic semiconductor compound may be 2.0 eV or more, preferably 2.4 eV or more, and particularly preferably 2.6 eV or more. This is because when the band gap of the inorganic semiconductor compound is in the above range, the light transmittance in the visible region of the mixed semiconductor layer can be increased. In addition, if the band gap is too small, the mixed semiconductor layer may be colored, which may reduce the light transmittance in the visible region. On the other hand, as described above, the upper limit value of the band gap of the inorganic semiconductor compound is not particularly limited because the light transmission increases as the band gap increases, but it is usually set to 8 eV or less.

As such an inorganic semiconductor compound, for example, a compound containing at least one element selected from elements of Group 12 to Group 16 of the Group 18 element periodic table can be cited. Specifically, ZnS, ZnSe, ZnTe, GaN, GaS, Ga ₂ S ₃ , GaP, GaSe, AlN, AlP, AlAs, AlSb, Al ₂ Se ₃ , BN, BP, BAs, CdS, HgS, SiC, etc. Can be mentioned. These compounds may be used alone or in combination of two or more. In this embodiment, among the above, at least one compound selected from ZnS, ZnSe, GaN, and GaS is preferably used, and ZnS or ZnSe is particularly preferable. This is because the above compound has a large band gap and is transparent.

  In addition, as described above, the light-transmitting insulating compound is a layer having a protective function that reduces the impact on the organic EL layer or the charge injecting and transporting layer when the second electrode layer is formed. If it is possible, there is no particular limitation. In addition, the band gap of the insulating compound may be 2.0 eV or more, but since the insulating property is exhibited, a band gap of 8 eV or more is usually used. Further, the upper limit value of the band gap of the insulating compound is not particularly limited since the light transmission increases as the band gap increases, as described above, but is usually 30 eV or less. When the band gap of the insulating compound is in the above range, the light transmittance in the visible region of the mixed semiconductor layer can be increased.

As such an insulating compound, for example, a metal compound containing at least one element selected from Group 17 elements of the Group 18 element periodic table can be given. Specific examples include alkali metal, alkaline earth metal, rare earth element or transition element fluorides, chlorides, bromides, and iodides. More specifically, LiF, NaF, KF, MgF ₂ , CaF ₂ , BaF ₂ , LaF ₃ , AlF ₃ , ZnF ₂ , CuF ₂ , LiCl, RbCl, MgCl ₂ , BeCl ₂ , NaBr, GeBr, NaI, KI Etc. These compounds may be used alone or in combination of two or more. In this embodiment, it is preferable to use alkali metal, alkaline earth metal, rare earth element or transition element fluoride, and it is particularly preferable to use LiF, MgF ₂ or CaF ₂ .

(metal)
The metal used in this embodiment is not particularly limited as long as it has a function of transporting and injecting charges into the organic EL layer as described above, but the electrical resistivity ρ is less than 1 × 10 ⁻⁵ Ω · cm. In particular, it is preferably 3 × 10 ⁻⁶ Ω · cm or less, more preferably 1 × 10 ⁻⁶ Ω · cm or less. This is because the electrical conductivity of the mixed semiconductor layer can be increased when the electrical resistivity of the metal is in the above range.

  Examples of such metals include alkali metals (Li, Na, K, Rb, Cs, Fr), alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra), transition metals (Cu, Ag, Au). , Cr, Fe, Mo, Mn, Ni, Ta, W, Pt, Ti, Os), rare earth metals (Sc, Y, Eu, Er, Yb), Al, Ga, In, Zn, and the like. . These metals may be used independently and may use 2 or more types together. In this embodiment, among the above, it is preferable to use an alkali metal, an alkaline earth metal, Cu, Ag, Au, or Al, and it is particularly preferable to use an alkali metal or an alkaline earth metal. When an alkali metal or alkaline earth metal is used as the metal, for example, as described later, when an electron injection layer is formed between the light emitting layer and the mixed semiconductor layer, the electron injection layer is generally an alkali metal or alkaline earth metal. This is because the type of material used for producing the organic EL element can be reduced, and the manufacturing process becomes simple. For example, when the second electrode layer is a cathode, the alkali metal or the alkaline earth metal has a small work function value, so that these metals can make good electron injection by directly contacting the organic EL layer. Because. On the other hand, when Cu, Ag, Au, or Al is used as the metal, these metals have a large work function of 4.0 eV or more. Therefore, when the second electrode layer is an anode, the positive electrode injected from the second electrode layer This is because the holes can be stably injected into the light emitting layer.

  In this embodiment, the metal is not particularly limited as long as it is dispersed in the mixed semiconductor layer, and the metal may be dispersed uniformly or non-uniformly. In particular, when the metal is an alkali metal or an alkaline earth metal, it is preferable that a large amount of metal is unevenly distributed on the organic EL layer side and almost no metal is present on the second electrode layer side. Alkali metals and alkaline earth metals are highly reactive metals and therefore are easily oxidized. If a large amount of alkali metals and alkaline earth metals are present on the second electrode layer side, oxygen is introduced during film formation of the second electrode layer. Alternatively, it is easily oxidized by releasing oxygen from the target, and the current density and luminance characteristics of the organic EL element may be deteriorated.

  The content of the metal can be set in the range of usually 0.0001% to 90% by volume in the mixed semiconductor layer, preferably 0.01% to 60% by volume, and more preferably 0.1% by volume. % To 50% by volume, particularly 1% to 20% by volume is preferable. This is because if the content of the metal is too large, the light transmittance of the mixed semiconductor layer may be lowered. Conversely, if the content of the metal is too small, the effect of increasing the electrical conductivity of the mixed semiconductor layer may not be obtained.

  The metal content can be measured using X-ray photoelectron spectroscopy (XPS) or Rutherford backscattering analysis (RBS).

  Further, when the metal contained in the mixed semiconductor layer is a layer made of only a metal, the thickness of the layer made of only the metal is preferably 100 nm or less, and in particular, 1 nm to 30 nm, more preferably 1 nm to 20 nm, In particular, it is preferably in the range of 1 nm to 10 nm. It is because the light transmittance of a mixed semiconductor layer may fall when the thickness of the layer which consists only of the said metal is too thick. On the contrary, if the thickness of the layer made of only the metal is too thin, the conductivity of the semiconductor buffer layer may be lowered.

Note that the thickness of the layer made of only the metal can be calculated from the metal content in the mixed semiconductor layer and the volume and area of the mixed semiconductor layer. in this case,
(Thickness of the layer consisting only of metal) = (Volume of mixed semiconductor layer) × (Metal content) ÷ (Area of mixed semiconductor layer)
It becomes. In addition, the thickness of the layer made of only the metal can be calculated from the deposition rate and the deposition time when the mixed semiconductor layer is deposited. For example, when co-depositing a mixed semiconductor layer,
(Thickness of the layer consisting only of metal) = (Metal vapor deposition rate) × (Vapor deposition time)
It becomes.

(Semiconductor buffer layer)
The semiconductor buffer layer in this embodiment preferably has an average light transmittance of 30% or more in the visible region of 380 to 780 nm, and more preferably 50% or more. Thereby, even if it is a case where light is taken out from the 2nd electrode layer side, it is because light is not shielded. In addition, the said average light transmittance shall be the value measured in room temperature and air | atmosphere using the ultraviolet visible spectrophotometer (Corporation | KK Shimadzu Corporation UV-2200A).

Moreover, it is preferable that the electrical resistivity of the semiconductor buffer layer is a value between the electrical resistivity of the second electrode layer and the electrical resistivity of the organic EL layer. This is because charges injected from the second electrode layer can be efficiently injected into the organic EL layer. Specifically, the electrical resistivity of the semiconductor buffer layer is 1 × 10 ⁻⁴ Ω · cm to 1 × 10 ³ Ω · cm, especially 1 × 10 ⁻⁴ Ω · cm to 1 × 10 ² Ω · cm, particularly 1 It is preferably within the range of × 10 ⁻⁴ Ω · cm to 10 Ω · cm. The electrical resistivity is a value measured by a four-probe method using Dia Instruments Loresta-GP (MCP-T600).

  The thickness of the semiconductor buffer layer is not particularly limited as long as it satisfies the above average light transmittance and the above electrical resistivity. Specifically, the thickness is preferably in the range of 1 nm to 500 nm, and more preferably 1 nm. It is preferably in the range of ˜100 nm, particularly 10 nm to 50 nm. This is because if the thickness of the semiconductor buffer layer is too thick, the light transmittance may decrease. Conversely, if the thickness of the semiconductor buffer layer is too thin, there is a possibility that the effect of protecting the organic EL layer or the charge injecting and transporting layer from impact during film formation of the second electrode layer may not be obtained.

  The method for forming the semiconductor buffer layer in this embodiment is not particularly limited as long as it does not affect the organic EL layer. For example, the vacuum evaporation method, the high frequency sputtering method, the magnetron sputtering method, the ion beam sputtering method, the ion plate method, and the like. In particular, it is preferable to use a vacuum deposition method. For example, even if an electron injection layer is formed between the semiconductor buffer layer and the light emitting layer, oxygen is not normally introduced by the vacuum deposition method, so the metal contained in the electron injection layer when forming the semiconductor buffer layer This is because there is no risk of oxidation. Examples of such vacuum vapor deposition include resistance heating vapor deposition, electron beam vapor deposition, and flash vapor deposition. In particular, a one-source evaporation method, a two-source evaporation method or a three-source evaporation method using a resistance heating evaporation method or an electron beam evaporation method is preferable. On the other hand, when a high frequency sputtering method, a magnetron sputtering method, an ion beam sputtering method, or an ion plating method is used, it is preferable that oxygen is not introduced for the reasons described above. At this time, instead of oxygen, a rare gas such as argon, nitrogen, or the like may be introduced, and it is particularly preferable to introduce argon.

(Ii) Second Aspect A second aspect of the semiconductor buffer layer used in this embodiment has an inorganic layer made of an inorganic compound and a metal layer made of a metal, and the metal layer is an inorganic layer. It is formed between the middle layer or the inorganic layer and the second electrode layer. For example, in FIG. 2, the semiconductor buffer layer 4 has a configuration in which an inorganic layer 14a, a metal layer 14b, and an inorganic layer 14b are laminated in this order. In this aspect, since the semiconductor buffer layer has a metal layer made of a metal, the electrical resistivity of the semiconductor buffer layer as a whole can be lowered, and a decrease in current density-voltage characteristics can be suppressed. .

As the formation position of the inorganic layer and the metal layer in this embodiment, for example, the metal layer 14b may be formed so as to be sandwiched between the inorganic layers 14a as shown in FIG. 2, and the metal layer 14b as shown in FIG. However, it may be formed between the inorganic layer 14 a and the second electrode layer 5. Further, it is sufficient that the metal layer does not contact the organic EL layer, and a plurality of metal layers and a plurality of inorganic layers may be laminated.
Hereinafter, each structure of such a semiconductor buffer layer will be described.

(Inorganic layer)
The inorganic layer used in this embodiment is a layer made of an inorganic compound. In this embodiment, an inorganic semiconductor compound having a predetermined band gap can be used as the inorganic compound. Note that the inorganic semiconductor compound is the same as that described in the first embodiment, and thus the description thereof is omitted here.

  The thickness of the inorganic layer is not particularly limited as long as it can protect the organic EL layer from impact during the formation of the second electrode layer when the entire semiconductor buffer layer is formed. For example, as shown in FIG. 2, when the metal layer 14b is sandwiched between the inorganic layers 14a, the metal layer 14b is formed so as not to contact the organic EL layer 3 in this embodiment. The thickness of the provided inorganic layer 14a can be set to about 1 nm to 500 nm.

  Further, the method for forming the inorganic layer is not particularly limited as long as it does not affect the organic EL layer. For example, the vacuum deposition method, the high frequency sputtering method, the magnetron sputtering method, the ion beam sputtering method, the ion plating method, and the like. A method such as a vacuum evaporation method is preferably used. For example, even when an electron injection layer is formed between the semiconductor buffer layer and the light-emitting layer, oxygen is not normally introduced by the vacuum deposition method, so that the metal contained in the electron injection layer is not formed when forming the inorganic layer. This is because there is no risk of oxidation. Examples of such vacuum vapor deposition include resistance heating vapor deposition, electron beam vapor deposition, and ion beam vapor deposition. In particular, a one-source evaporation method, a two-source evaporation method or a three-source evaporation method using a resistance heating evaporation method or an electron beam evaporation method is preferable. On the other hand, when a high frequency sputtering method, a magnetron sputtering method, an ion beam sputtering method, or an ion plating method is used, it is preferable that oxygen is not introduced for the reasons described above. At this time, instead of oxygen, a rare gas such as argon, nitrogen, or the like may be introduced, and it is particularly preferable to introduce argon.

(Metal layer)
The metal layer used in this embodiment is a layer made of metal. The metal used for the metal layer is not particularly limited as long as it can lower the electrical resistivity of the entire semiconductor buffer layer, and has the electrical resistivity as described in the first aspect. It is preferable that

  In this embodiment, for example, when the metal layer 14b is sandwiched between the inorganic layers 14a as shown in FIG. 2, examples of the metal used include alkali metal (Li, Na, K, Rb, Cs, Fr), alkaline earth Metals (Be, Mg, Ca, Sr, Ba, Ra), transition metals (Cu, Ag, Au, Cr, Fe, Mo, Mn, Ni, Ta, W, Pt, Ti, Os), rare earth metals (Sc Y, Eu, Er, Yb), Al, Ga, In, Zn, and the like. These metals may be used independently and may use 2 or more types together.

  In addition, for example, when the metal layer 14b is formed between the inorganic layer 14a and the second electrode layer 5 as shown in FIG. It is preferable to use a metal having a function of about 4.0 to 5.5 eV. Examples of such metals include Ag, Au, Al, Cr, Cu, Fe, Mo, Mn, Ni, Ta, and W. Moreover, these metals may be used independently and may use 2 or more types together. Since these metals have low reactivity and are not easily oxidized by introducing oxygen or releasing oxygen from the target during the formation of the second electrode layer, the durability of the organic EL element can be increased.

  The thickness of the metal layer is preferably 100 nm or less, more preferably 1 nm to 30 nm, more preferably 1 nm to 20 nm, and particularly preferably 1 nm to 10 nm. This is because if the thickness of the metal layer is too thick, the light transmittance of the semiconductor buffer layer may decrease. Conversely, if the thickness of the metal layer is too thin, the conductivity of the semiconductor buffer layer may be lowered.

  The metal layer is not particularly limited as long as it does not affect the organic EL layer. For example, a vacuum deposition method, a high frequency sputtering method, a magnetron sputtering method, an ion beam sputtering method, an ion plating method, or the like is used. Among them, it is preferable to use a vacuum evaporation method. For example, even when an electron injection layer is formed between the semiconductor buffer layer and the light-emitting layer, oxygen is not normally introduced in the vacuum deposition method, so that the metal contained in the electron injection layer is not formed when the metal layer is formed. This is because there is no risk of oxidation. Examples of such vacuum vapor deposition include resistance heating vapor deposition, electron beam vapor deposition, and ion beam vapor deposition. In particular, a one-source evaporation method, a two-source evaporation method or a three-source evaporation method using a resistance heating evaporation method or an electron beam evaporation method is preferable. On the other hand, when a high frequency sputtering method, a magnetron sputtering method, an ion beam sputtering method, or an ion plating method is used, it is preferable that oxygen is not introduced for the reasons described above. At this time, instead of oxygen, a rare gas such as argon, nitrogen, or the like may be introduced, and it is particularly preferable to introduce argon.

  Since other points of the semiconductor buffer layer are the same as those described in the first aspect, description thereof is omitted here.

(Iii) Third Aspect A third aspect of the semiconductor buffer layer used in the present embodiment has a mixed semiconductor layer in which a metal is dispersed in an inorganic compound and an inorganic layer made of an inorganic compound. In this aspect, since the mixed semiconductor layer constituting the semiconductor buffer layer is a metal dispersed in an inorganic compound, it is possible to suppress a decrease in current density-voltage characteristics.

  The formation position of the mixed semiconductor layer and the inorganic layer in this embodiment is not particularly limited, and may be laminated in the order of the mixed semiconductor layer and the inorganic layer from the organic EL layer side. You may laminate | stack in order. A plurality of mixed semiconductor layers and inorganic layers may be stacked.

  The other points of the mixed semiconductor layer and the semiconductor buffer layer are the same as those described in the first aspect, and the inorganic layer is the same as that described in the second aspect. Description of is omitted.

(Iv) Fourth Aspect A fourth aspect of the semiconductor buffer layer used in the present embodiment has a mixed semiconductor layer in which a metal is dispersed in an inorganic compound and a metal layer made of a metal. In this aspect, the mixed semiconductor layer constituting the semiconductor buffer layer is a metal dispersed in an inorganic compound, and the semiconductor buffer layer has a metal layer made of metal, so that the semiconductor buffer layer as a whole The electrical resistivity can be lowered, and the decrease in current density-voltage characteristics can be suppressed.

  The formation position of the mixed semiconductor layer and the metal layer in this embodiment is not particularly limited, and the mixed semiconductor layer and the metal layer may be stacked in this order from the organic EL layer side. You may laminate | stack in order. A plurality of mixed semiconductor layers and metal layers may be stacked.

  Hereinafter, each structure of such a semiconductor buffer layer will be described. The mixed semiconductor layer is the same as that described in the first aspect, and a description thereof is omitted here.

(Metal layer)
The metal layer used in this embodiment is a layer made of metal. The metal used for the metal layer is not particularly limited as long as it can lower the electrical resistivity of the entire semiconductor buffer layer, and has the electrical resistivity as described in the first aspect. It is preferable that

  Examples of the metal used in the metal layer in this embodiment include alkali metals (Li, Na, K, Rb, Cs, Fr), alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra), transition metals ( Cu, Ag, Au, Cr, Fe, Mo, Mn, Ni, Ta, W, Pt, Ti, Os), rare earth metals (Sc, Y, Eu, Er, Yb), Al, Ga, In, Zn, etc. Can be mentioned. These metals may be used independently and may use 2 or more types together.

  For example, when the metal layer is formed so as to be sandwiched between the mixed semiconductor layers, the metal is preferably an alkali metal or an alkaline earth metal. For example, as will be described later, when an electron injection layer is formed between the organic EL layer and the semiconductor buffer layer, the electron injection layer is generally formed using an alkali metal or an alkaline earth metal. This is because the number of types of materials used for manufacturing the can be reduced, and the manufacturing process becomes simple.

  For example, when the metal layer is formed in contact with the second electrode layer, it is preferable to use a metal having a work function of about 4.0 to 5.5 eV. Examples of such metals include Ag, Au, Al, Cr, Cu, Fe, Mo, Mn, Ni, Ta, and W. Moreover, these metals may be used independently and may use 2 or more types together. Since these metals have low reactivity and are not easily oxidized by introducing oxygen or releasing oxygen from the target during the formation of the second electrode layer, the durability of the organic EL element can be increased.

  Furthermore, for example, when the metal layer is formed so as to be in contact with the organic EL layer, a preferable metal differs depending on the type (anode, cathode) of the second electrode layer described later. When the second electrode layer is a cathode, the metal is preferably an alkali metal or an alkaline earth metal. This is because electrons can be stably injected into the organic EL layer. Further, as described above, when the electron injection layer is formed between the organic EL layer and the semiconductor buffer layer, the electron injection layer is generally formed using an alkali metal or an alkaline earth metal. This is because the number of types of materials used for manufacturing the can be reduced, and the manufacturing process becomes simple. On the other hand, when the second electrode layer is an anode, the metal preferably has a work function of about 4.0 to 5.5 eV, specifically Ag, Au, Al, Cr, Cu, Fe, Mo. , Mn, Ni, Ta, W, etc. are preferably used. This is because holes can be stably injected into the organic EL layer.

  In addition, since it is the same as that of what was described in the said 2nd aspect about the other point of a metal layer, description here is abbreviate | omitted. Further, since other points of the semiconductor buffer layer are the same as those described in the first aspect, description thereof is omitted here.

(V) Others In addition to the configuration described above, the semiconductor buffer layer in the present embodiment may be a stacked layer of a mixed semiconductor layer, a metal layer, and an inorganic layer. In this case, the formation position of the mixed semiconductor layer, the metal layer, and the inorganic layer is not particularly limited. For example, a layer in which a mixed semiconductor layer, a metal layer, and an inorganic layer are stacked in this order from the organic EL layer side, a layer in which an inorganic layer, a mixed semiconductor layer, and a metal layer are stacked in this order can be used.

  Further, in the semiconductor buffer layer used in the present embodiment, the metal is diffused (exists) in the entire semiconductor buffer layer in the mixed buffer layer rather than the laminated inorganic layer and metal layer. Therefore, electrical conductivity is increased.

(2) Organic EL layer Next, the organic EL layer used in this embodiment will be described. The organic EL layer used in this embodiment is formed between the semiconductor buffer layer and a first electrode layer described later.

  The organic EL layer in this embodiment is composed of one or a plurality of organic layers including at least a light emitting layer. That is, the organic EL layer is a layer including at least a light emitting layer, and the layer configuration is a layer having one or more organic layers. Usually, when an organic EL layer is formed by a wet method by coating, it is often difficult to stack a large number of layers in relation to a solvent, so that it is often formed of one or two organic layers. However, it is possible to further increase the number of layers by devising an organic material so that the solubility in a solvent is different or by combining a vacuum deposition method.

Examples of the organic layer formed in the organic EL layer other than the light emitting layer include charge injection layers such as a hole injection layer and an electron injection layer. Furthermore, examples of the other organic layers include a charge transport layer such as a hole transport layer that transports holes to the light-emitting layer and an electron transport layer that transports electrons to the light-emitting layer. In many cases, it is formed integrally with the charge injection layer by imparting a charge transporting function. In addition, as an organic layer formed in the organic EL layer, it prevents holes or electrons from penetrating like a carrier block layer and further prevents diffusion of excitons and confines excitons in the light emitting layer. And a layer for increasing the recombination efficiency.
Hereinafter, the light emitting layer which is an essential component in such an organic EL layer will be described.

(I) Light-Emitting Layer The light-emitting layer used in this embodiment has a function of emitting light by providing a recombination field between electrons and holes. As the material for forming the light emitting layer, a dye-based light-emitting material, a metal complex-based light-emitting material, or a polymer-based light-emitting material can be generally used.

  Examples of dye-based light emitting materials include cyclopentadiene derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silole derivatives, thiophene ring compounds, pyridine rings Examples thereof include compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, coumarin derivatives, oxadiazole dimers, pyrazoline dimers, and the like.

  Metal complex light emitting materials include aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethyl zinc complex, porphyrin zinc complex, europium complex, iridium metal complex, platinum metal complex, etc. The metal has Al, Zn, Be, Ir, Pt, etc., or a rare earth metal such as Tb, Eu, Dy, etc., and the ligand has an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure, etc. A metal complex etc. can be mentioned. Specifically, tris (8-quinolinolato) aluminum complex (Alq3) can be used.

  Furthermore, as the polymer light emitting material, polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyvinylcarbazole, polyfluorenone derivatives, polyfluorene derivatives, polyquinoxaline derivatives, polydialkylfluorene derivatives, And copolymers thereof. Moreover, what polymerized the said pigment-type luminescent material and metal complex type | system | group luminescent material is also mentioned.

  Among the above, the light emitting material used in the present embodiment is preferably a metal complex light emitting material or a polymer light emitting material, and more preferably a polymer light emitting material. Of the polymer light emitting materials, a conductive polymer having a π-conjugated structure is preferable. Examples of the conductive polymer having such a π-conjugated structure include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorenone derivatives, polyfluorene derivatives, polyquinoxaline derivatives as described above. , Polydialkylfluorene derivatives, and copolymers thereof.

  The thickness of the light emitting layer is not particularly limited as long as it can provide a function of emitting light by providing a recombination field between electrons and holes, and is, for example, about 1 nm to 200 nm. it can.

  Further, a dopant that emits fluorescence or phosphorescence may be added to the light emitting layer for the purpose of improving the light emission efficiency and changing the light emission wavelength. Examples of such dopants include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazoline derivatives, decacyclene, phenoxazone, quinoxaline derivatives, carbazole derivatives, fluorene derivatives, and the like. Can be mentioned.

  In this embodiment, it is possible to combine light emitting layers that emit different colors, and patterning is required when manufacturing full-color and multi-color displays.

  The method for forming the light emitting layer is not particularly limited as long as it is a method capable of high-definition patterning. For example, vapor deposition method, printing method, inkjet method, spin coating method, casting method, dipping method, bar coating method, blade coating method, roll coating method, gravure coating method, flexographic printing method, spray coating method, and self-assembly method (Alternate adsorption method, self-assembled monolayer method) and the like. Among these, it is preferable to use a vapor deposition method, a spin coating method, and an ink jet method. Further, when the light emitting layer is patterned, it may be applied separately by a masking method for pixels having different light emission colors, or a partition may be formed between the light emitting layers. As a material for forming such a partition, a photocurable resin such as a photosensitive polyimide resin or an acrylic resin, a thermosetting resin, an inorganic material, or the like can be used. Furthermore, you may perform the process which changes the surface energy (wetting property) of the material which forms these partition walls.

(3) 1st electrode layer Next, the 1st electrode layer used for this embodiment is demonstrated. The 1st electrode layer used for this embodiment is formed between the above-mentioned organic EL layer and the base material mentioned below, and is formed as an electrode which counters the 2nd electrode layer mentioned below. The first electrode layer may be an anode or a cathode, and may be transparent or translucent, or not transparent or translucent. For example, when extracting light from the substrate side, the first electrode layer is required to be transparent or translucent. When extracting light from the second electrode layer side, the first electrode layer is transparent or translucent. It does not have to be. Moreover, when taking out light from both sides of the base material side and the second electrode layer side, both the first electrode layer and the second electrode layer are required to be transparent or translucent.

  The material for forming the first electrode layer is not particularly limited as long as it is a conductive material. For example, Au, Ta, W, Pt, Ni, Pd, Cr, Cu, Mo, alkali metal, alkaline earth metal, etc. Metals, oxides of these metals, Al alloys such as AlLi, AlCa and AlMg, Mg alloys such as MgAg, alloys such as Ni alloys, Cr alloys, alkali metal alloys, and alkaline earth metal alloys be able to. These conductive materials may be used alone, in combination of two or more kinds, or may be laminated using two or more kinds. Further, as the conductive material, conductive inorganic oxides such as In—Sn—O, In—Zn—O, In—O, Zn—O, Zn—O—Al, and Zn—Sn—O, metal doped Conductive polymers such as polythiophene, polyaniline, polyacetylene, polyalkylthiophene derivatives, and polysilane derivatives, α-Si, α-SiC, and the like can also be used.

  In this embodiment, the first electrode layer may be an anode or a cathode, but usually the first electrode layer is formed as an anode. When the first electrode layer is formed as an anode, a conductive material having a large work function value is preferably used so that holes can be easily injected. Among these, it is preferable to use at least one selected from the group consisting of metals having a work function of 4.5 eV or more, alloys of such metals, and the above-described conductive inorganic oxides. This is because if the work function of the metal is less than 4.5 eV, the hole injection efficiency may decrease.

  In order to increase the value of the work function of the first electrode layer, UV ozone treatment, oxygen plasma treatment, argon plasma treatment, or the like may be performed. For example, when oxygen plasma treatment is performed on the first electrode layer made of metal to oxidize only the outermost metal, the work function value increases, so that the hole injection efficiency can be improved. In this case, oxygen plasma treatment is performed only on the outermost surface of the first electrode layer. This is because when the thickness of the oxidized metal layer is increased, the layer becomes insulative. In addition, when the metal used for the first electrode layer is naturally oxidized, by performing argon plasma treatment, the oxidized metal present on the surface can be removed, so that the hole injection efficiency is improved. be able to.

  Furthermore, in order to prevent a short circuit and a leak current of the organic EL element, the first electrode layer may be subjected to mirror polishing. In the mirror polishing process, since the first electrode layer can be flattened, a short circuit or a leak current of the organic EL element can be prevented.

  When the first electrode layer is formed as a cathode, it is preferable to use a conductive material having a small work function value so that electrons can be easily injected. The conductive material having a small work function value may be any material having a work function value smaller than that of the conductive material used for the anode. However, as described above, the work function of the metal is less than 4.5 eV. Therefore, it is preferable to use at least one selected from the group consisting of metals having a work function of 4.2 eV or higher, alloys of such metals, and the above-described conductive inorganic oxides.

The specific resistance value of the first electrode layer is preferably 1 × 10 ⁻² Ω · cm or less, and more preferably 5 × 10 ⁻⁴ Ω · cm or less. It is because the circuit loss of the electric power by electrode resistance can be prevented because the specific resistance value of a 1st electrode layer is the said range. The specific resistance value is a value measured by a four-probe method using Dia Instruments Loresta-GP (MCP-T600).

  In the present embodiment, when taking out light from the substrate side, the first electrode layer is required to be transparent or translucent, and the specific light transmittance is an average light transmission in a visible region of 380 to 780 nm. The rate is preferably 50% or more, more preferably 80% or more, and particularly preferably 85% or more.

  Further, the thickness of the first electrode layer is not particularly limited as long as it satisfies the specific resistance value and the average light transmittance. The thickness varies depending on the conductive material used, for example, 40 nm to 500 nm. It is preferable to be within the range. If the thickness of the first electrode layer is too thin, the resistance may be increased. If the thickness of the first electrode layer is too thick, for example, a step present at the end of the first electrode layer formed in a pattern shape. As a result, the organic EL layer, the semiconductor buffer layer, the second electrode layer, or the like may be cut or disconnected, or the first electrode layer and the second electrode layer may be short-circuited.

  Examples of the method for forming the first electrode layer include a sputtering method, a vacuum heating vapor deposition method, an EB vapor deposition method, and an ion plating method.

(4) Second electrode layer Next, the second electrode layer used in this embodiment will be described. The second electrode layer used in the present embodiment is formed on the semiconductor buffer layer and is formed as an electrode facing the first electrode layer.

  The second electrode layer used in this embodiment may be an anode or a cathode, and may be transparent or translucent, or not transparent or translucent. For example, when extracting light from the second electrode layer side, the second electrode layer is required to be transparent or translucent. However, when extracting light from the substrate side, the second electrode layer is transparent or semi-transparent. It does not have to be transparent. Moreover, when taking out light from both sides of the base material side and the second electrode layer side, both the first electrode layer and the second electrode layer are required to be transparent or translucent.

  In addition, since the formation material, the specific resistance value, and the average light transmittance of the second electrode layer are the same as those described in the column of the first electrode layer, description thereof is omitted here.

  The thickness of the second electrode layer is not particularly limited as long as the specific resistance value and the average light transmittance are satisfied, and may vary depending on the conductive material used. For example, the thickness is in the range of 10 nm to 500 nm. It is preferable that This is because if the thickness of the second electrode layer is too thin, the conductivity may be insufficient. On the contrary, if the thickness of the second electrode layer is too thick, the light transmittance becomes insufficient, and when the organic EL element is deformed during or after the manufacturing process of the organic EL element, defects such as cracks are present. This is because it is likely to occur.

  Examples of the method for forming the second electrode layer include vacuum film formation methods such as sputtering, ion plating, and electron beam. In the present embodiment, since the semiconductor buffer layer is formed between the organic EL layer and the second electrode layer, the organic EL layer can be protected from an impact during the formation of the second electrode layer. Even if the organic EL layer contains a highly reactive metal, the semiconductor buffer layer prevents oxidation of the metal due to oxygen introduction or oxygen release from the target during the formation of the second electrode layer. In addition, it is possible to prevent deterioration of charge injection characteristics to the light emitting layer in the organic EL layer.

(5) Base Material Next, the base material used in this embodiment will be described. The material for forming the base material used in this embodiment is not particularly limited as long as it is a material having self-supporting properties. Moreover, when taking out light from the base material side, it needs to be transparent, but when taking out light from the 2nd electrode layer side, it does not need to have transparency.

  Examples of the material used for such a substrate include inorganic materials such as quartz, glass, silicon wafer, glass on which TFT (thin film transistor) is formed, or polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate. List polymer materials such as (PBT), polyphenylene sulfide (PPS), polyimide (PI), polyamideimide (PAI), polyethersulfone (PES), polyetherimide (PEI), polyetheretherketone (PEEK) Can do. Among these, quartz (glass), silicon wafer, or super engineering plastics such as polyimide (PI), polyamideimide (PAI), polyethersulfone (PES), polyetherimide (PEI), and polyetheretherketone (PEEK) It is preferable to use it. This is because these materials have a heat resistance of 200 ° C. or higher and can increase the substrate temperature in the production process. In particular, when an active drive display device using TFTs is manufactured, the above-mentioned materials can be preferably used because the temperature becomes high during the manufacturing process.

  In addition, when the above-described polymer material is used for the base material, the organic EL layer may be deteriorated by the gas generated from the polymer material. Therefore, the gas barrier layer is provided between the base material and the first electrode layer. Is preferably provided. Examples of such a gas barrier layer include silicon oxide and silicon nitride.

  Furthermore, what gave the micro lens process etc. which raise the light extraction efficiency to the base-material surface can also be used. In this case, the first electrode layer and the organic EL layer are formed on the surface opposite to the surface on which microlens processing or the like is performed.

  The thickness of the substrate is appropriately selected depending on the material to be used and the application of the organic EL element, and can be, for example, about 0.005 mm to 5 mm.

(6) Charge Injecting and Transporting Layer In this embodiment, for example, as shown in FIG. 4, between the light emitting layer in the organic EL layer 3 and the first electrode layer 2 or the light emitting layer in the organic EL layer 3. A charge injecting and transporting layer 6 can be formed between the semiconductor buffer layer 4 and the semiconductor buffer layer 4. The charge injecting and transporting layer here has a function of stably transporting the charge from the first electrode layer or the second electrode layer to the light emitting layer. By providing between one electrode layer or between the light emitting layer and the semiconductor buffer layer, the injection of charges into the light emitting layer is stabilized, and the light emission efficiency can be increased.

  As such a charge injecting and transporting layer, a hole injecting and transporting layer for transporting holes injected from the anode into the light emitting layer, and an electron injecting and transporting similarly for transporting electrons injected from the cathode into the light emitting layer. There is a layer. Hereinafter, the hole injection / transport layer and the electron injection / transport layer will be described.

(I) Hole Injecting and Transporting Layer The hole injecting and transporting layer used in this embodiment is not particularly limited as long as it is a layer that can transport holes injected from the anode into the light emitting layer. For example, a hole injection layer having a function of stably injecting holes injected from the anode into the light emitting layer, and a hole transport layer having a function of transporting holes injected from the anode into the light emitting layer It may be a case of having either one, a case of having both a hole injection layer and a hole transport layer, or a single layer having both functions of a hole injection function and a hole transport function It may be the case where it consists of.

  In this embodiment, the hole injecting and transporting layer is formed on the electrode layer side serving as the anode. For example, when the first electrode layer is an anode, the hole injection / transport layer is formed between the light emitting layer and the first electrode layer, and when the second electrode layer is the anode, hole injection is performed. The transport layer is formed between the light emitting layer and the semiconductor buffer layer.

  A material for forming such a hole injecting and transporting layer is not particularly limited as long as it is a material capable of stably transporting holes injected from the anode into the light emitting layer. For example, in addition to the compounds exemplified as the light emitting material for the light emitting layer, oxides such as phenylamine, starburst amine, phthalocyanine, vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide, amorphous carbon, polyaniline, polythiophene And derivatives such as polyphenylene vinylene. Specifically, bis (N- (1-naphthyl-N-phenyl) benzidine (α-NPD), 4,4,4-tris (3-methylphenylphenylamino) triphenylamine (MTDATA), poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS), polyvinyl carbazole (PVCz), or the like can be used.

  The thickness of the hole injection layer is not particularly limited as long as it is a thickness that sufficiently injects holes from the first electrode layer or the second electrode layer and transports holes to the light emitting layer. Specifically, it is preferably in the range of 0.5 nm to 300 nm, particularly in the range of 10 nm to 100 nm.

(Ii) Electron Injection / Transport Layer Next, the electron injection / transport layer used in this embodiment will be described. The electron injecting and transporting layer used in the present embodiment is not particularly limited as long as electrons injected from the cathode can be transported into the light emitting layer. For example, in the case of having either one of an electron injection layer having a function of stably injecting electrons injected from the cathode into the light emitting layer and an electron transport layer having a function of transporting electrons into the light emitting layer. It may be a case having both an electron injection layer and an electron transport layer, or a case of a single layer having both an electron injection function and an electron transport function.

  In this embodiment, the electron injecting and transporting layer is formed on the electrode layer side serving as the cathode. For example, when the first electrode layer is a cathode, the electron injection / transport layer is formed between the light emitting layer and the first electrode layer. When the second electrode layer is a cathode, the electron injection / transport layer is formed. Is formed between the light emitting layer and the semiconductor buffer layer.

  The material for forming the electron injection layer used in this embodiment is not particularly limited as long as it can stabilize the injection of electrons into the light emitting layer. For example, in addition to the compounds exemplified as the light emitting material of the light emitting layer, aluminum, strontium, calcium, lithium, cesium, magnesium oxide, aluminum oxide, strontium oxide, lithium oxide, lithium fluoride, magnesium fluoride, strontium fluoride, fluorine Alkali metal or alkaline earth metal, alkali metal or alkaline earth metal oxide, alkali metal or alkaline earth metal fluoride such as calcium fluoride, barium fluoride, cesium fluoride, polymethylmethacrylate polystyrene sodium sulfonate, etc. And organic complexes of alkali metals. Among them, it is preferable to use an alkaline earth metal fluoride. This is because the alkaline earth metal fluoride can improve the stability and life of the organic EL layer. This is because the alkaline earth metal fluoride is less reactive with water than the above-mentioned alkali metal compounds and alkaline earth metal oxides, and during or after the formation of the electron injection layer. This is because there is little water absorption. Furthermore, the alkaline earth metal fluoride has a higher melting point and superior heat stability than the alkali metal compounds described above.

  Conventionally, for example, when an alkali metal, an alkaline earth metal, or a rare earth metal is used as the electron injection layer and the electron injection layer is formed between the light emitting layer and the second electrode layer, the metal is easily oxidized. In some cases, the metal used for the electron injection layer is oxidized by oxygen introduction or oxygen release from the target during the formation of the second electrode layer, and the electron injection function is lost. On the other hand, in this embodiment, since the semiconductor buffer layer is formed between the light emitting layer and the second electrode layer, the electron injection layer is formed between the light emitting layer and the semiconductor buffer layer. However, since the electron injection layer is protected by the semiconductor buffer layer when the second electrode layer is formed, oxidation of the metal used for the electron injection layer can be prevented.

  The thickness of the electron injection layer is preferably in the range of about 0.2 nm to 10 nm because the above-described alkali metal or alkaline earth metal compound is insulative.

  In addition, when a transparent conductive material such as In—Zn—O is used as the cathode, these work functions are 4.6 eV or more, and therefore materials having a work function of 4.0 eV or less are used. It is preferable to form an electron injection layer. Under a low driving voltage, it is difficult to inject electrons directly from the cathode made of In—Zn—O having a work function of 4.6 eV or more into the light emitting layer, but between the cathode and the light emitting layer, it is 4.0 eV or less. This is because providing an electron injection layer having a work function facilitates injection of electrons. Examples of such a material having a work function of 4.0 eV or less include Ba, Ca, Li, Cs, and Mg. When the electron injection layer is formed of such a material, the thickness of the electron injection layer is preferably in the range of 0.2 nm to 50 nm, particularly 0.2 nm to 20 nm. In this case, since a transparent conductive material is used as the cathode, it is possible to extract light from the cathode side, and when extracting light from the cathode side, the electron injection layer is also required to be transparent. is there. If the thickness of the electron injection layer is too thick, the transparency may decrease.

  The material for forming the electron transport layer used in this embodiment is not particularly limited as long as it is a material capable of transporting electrons injected from the cathode or the electron injection layer into the light emitting layer. For example, examples of the electron-transporting organic material include BCP (basocupron), Bpehn (vasophenanthroline), a phenanthroline derivative, and a tris (8-quinolinolato) aluminum complex (Alq3).

  When the electron injecting and transporting layer used in this embodiment is a single layer having both the electron injecting function and the electron transporting function, the electron transporting organic material is doped with an alkali metal or an alkaline earth metal. A metal doped layer can be used. Examples of the electron-transporting organic material include bathocuproin (BCP) and bathophenanthroline (Bphen). Examples of the metal to be doped include Li, Cs, Ba, and Sr. The electron transporting organic material, metal, and molar ratio in the metal doped layer are preferably in the range of 1: 1 to 3, and more preferably in the range of 1: 1 to 2. The thickness of such a metal doped layer is preferably in the range of 5 nm to 500 nm, and more preferably in the range of 10 nm to 100 nm. Since the metal doped layer has a high electron mobility and a high light transmittance as compared with a single metal, the metal doped layer can be made thicker than the electron injection layer.

(Iii) Others In this embodiment, the semiconductor buffer layer described above (first to fourth embodiments), the type of metal contained in the semiconductor buffer layer, and the type of the second electrode layer (anode) In some cases, it may be preferable to form a charge injecting and transporting layer. Hereinafter, each aspect of the semiconductor buffer layer will be described.

(When the semiconductor buffer layer is the first embodiment)
This embodiment is a case where the semiconductor buffer layer is a mixed semiconductor layer.
In this embodiment, when the second electrode layer is a cathode, Cu, Ag, Au, Al, or the like having a work function of 4.0 eV or more is used as the metal contained in the mixed semiconductor. The energy barrier at the interface with the light emitting layer becomes high, and it may be difficult to inject electrons directly from the mixed semiconductor layer to the light emitting layer under a low voltage. Therefore, when the second electrode layer is a cathode and the work function of the metal contained in the mixed semiconductor layer is 4.0 eV or more, an electron injecting and transporting layer is provided between the mixed semiconductor layer and the light emitting layer. Is preferably provided. At this time, when taking out light from the second electrode layer side, the electron injecting and transporting layer preferably has sufficient light transmittance.

  On the other hand, when alkali metal or alkaline earth metal is used as the metal contained in the mixed semiconductor, since these metals have a work function as small as 4.0 eV or less, electrons injected from the second electrode layer are emitted from the light emitting layer. Can be injected stably. Therefore, when the second electrode layer is a cathode and the metal contained in the mixed semiconductor layer is an alkali metal or an alkaline earth metal, an electron injecting and transporting layer is provided between the mixed semiconductor layer and the light emitting layer. May not be provided.

  In this embodiment, when the second electrode layer is an anode, when an alkali metal or an alkaline earth metal is used as the metal contained in the mixed semiconductor layer, these metals have a work function of 4.0 eV or less. Therefore, the energy barrier at the interface between the mixed semiconductor layer and the light emitting layer increases, and it may be difficult to inject holes directly from the mixed semiconductor layer to the light emitting layer under a low voltage. Therefore, when the second electrode layer is an anode and the metal contained in the mixed semiconductor layer is an alkali metal or an alkaline earth metal, hole injection transport is performed between the mixed semiconductor layer and the light emitting layer. It is preferable to provide a layer. At this time, when extracting light from the second electrode layer side, the hole injecting and transporting layer preferably has sufficient light transmittance.

  On the other hand, when Cu, Ag, Au, Al, or the like having a work function of 4.0 eV or more is used as the metal contained in the mixed semiconductor layer, holes injected from the second electrode layer are stably supplied to the light emitting layer. Can be injected. Therefore, when the second electrode layer is an anode and the work function of the metal contained in the mixed semiconductor layer is 4.0 eV or more, hole injection transport is performed between the mixed semiconductor layer and the light emitting layer. It is not necessary to provide a layer.

(When the semiconductor buffer layer is the second mode)
This embodiment is a case where the semiconductor buffer layer has an inorganic layer and a metal layer. In this embodiment, it is preferable to provide a charge injection layer between the light emitting layer and the semiconductor buffer layer. In this case, since the metal layer is formed so as not to be in contact with the organic EL layer, there is a possibility that charge injection is insufficient. However, a charge injection layer is provided between the light emitting layer and the semiconductor buffer layer. This is because charges can be efficiently injected into the light emitting layer. At this time, when taking out light from the second electrode layer side, the charge injecting and transporting layer preferably has sufficient light transmittance.

(When the semiconductor buffer layer is the third aspect)
This embodiment is a case where the semiconductor buffer layer has a mixed semiconductor layer and an inorganic layer.
In this embodiment, when the inorganic layer is formed so as to be in contact with the organic EL layer, a charge injection layer is preferably provided between the light emitting layer and the inorganic layer. In this case, since the metal contained in the mixed semiconductor layer is not in contact with the organic EL layer, the charge injection may be insufficient. However, a charge injection layer is provided between the light emitting layer and the inorganic layer. This is because charges can be efficiently injected into the light emitting layer. At this time, when taking out light from the second electrode layer side, the charge injecting and transporting layer preferably has sufficient light transmittance.

  In this embodiment, the mixed semiconductor layer is formed in contact with the organic EL layer, the second electrode layer is a cathode, and the metal contained in the mixed semiconductor layer is an alkali metal or alkaline earth. In the case of a similar metal, an electron injecting and transporting layer may not be provided between the mixed semiconductor layer and the light emitting layer. This is because these metals have a work function as small as 4.0 eV or less, so that electrons injected from the second electrode layer can be stably injected into the light emitting layer.

  Further, in this embodiment, the mixed semiconductor layer is formed in contact with the organic EL layer, the second electrode layer is an anode, and the metal contained in the mixed semiconductor layer is Cu as described above. , Ag, Au, Al, or the like, it is not necessary to provide a hole injecting and transporting layer between the mixed semiconductor layer and the light emitting layer. This is because these metals have a work function as large as 4.0 eV or more, so that holes injected from the second electrode layer can be stably injected into the light emitting layer.

(When the semiconductor buffer layer is the fourth aspect)
This embodiment is a case where the semiconductor buffer layer has a mixed semiconductor layer and a metal layer.
In this embodiment, when the second electrode layer is a cathode and the metal contained in the mixed semiconductor layer and the metal EL layer in contact with the organic EL layer is an alkali metal or an alkaline earth metal, the semiconductor It is not necessary to provide an electron injecting and transporting layer between the buffer layer and the light emitting layer. This is because these metals have a work function as small as 4.0 eV or less, so that electrons injected from the second electrode layer can be stably injected into the organic EL layer.

  Further, in this embodiment, the second electrode layer is an anode, and the metal contained in the layer in contact with the organic EL layer among the mixed semiconductor layer and the metal layer is a Cu having a work function of 4.0 eV or more. In the case of Ag, Au, Al, etc., it is not necessary to provide a hole injecting and transporting layer between the semiconductor buffer layer and the light emitting layer. This is because holes injected from the second electrode layer can be stably injected into the organic EL layer.

(7) Others In this embodiment, a color filter layer and / or a color conversion layer may be formed on the second electrode layer. Thereby, the color purity of the light of the light emitting layer in the organic EL layer can be corrected by color correction.

  The color filter layer can be, for example, a red colored layer, a green colored layer, and a blue colored layer. Each color filter layer is sensitive to one or more pigments such as azo, phthalocyanine, and anthraquinone pigments. It can be formed using a photosensitive resin composition prepared by dispersing in a resin.

  The color conversion layer can be, for example, a red conversion layer, a green conversion layer, and a blue conversion layer. Each color conversion layer is spin-coated with a coating liquid in which a desired fluorescent dye and resin are dispersed or solubilized. The film can be formed by applying a film by a coating method, a roll coating method, a cast coating method, or the like, and patterning the film by a photolithography method.

2. Second Embodiment Next, a second embodiment of the organic EL element of the present invention will be described. A second embodiment of the organic EL device of the present invention includes a base material, an electrode layer formed on the base material, an organic EL layer formed on the electrode layer and having at least a light emitting layer, and the organic It has a semiconductor electrode layer containing an inorganic compound and a metal formed on an EL layer and having a band gap of 2.0 eV or more.

  The organic EL element of this embodiment will be described with reference to the drawings. FIG. 5 is a schematic cross-sectional view showing an example of the organic EL element of this embodiment. In FIG. 5, the organic EL element includes a base material 21, an electrode layer 22 formed on the base material 21, an organic EL layer 23 formed on the electrode layer 22 and having at least a light emitting layer, and the organic An electron injection layer 26 formed on the EL layer 23 and a semiconductor electrode layer 24 formed on the electron injection layer 26 are included.

According to this embodiment, since the semiconductor electrode layer is formed by, for example, a vacuum deposition method, the organic EL layer is not shocked when the semiconductor electrode layer is formed, and the light emission characteristics of the organic EL element are reduced. It can be avoided. Further, even when an electron injection layer is formed between the light emitting layer and the semiconductor electrode layer, oxygen is not normally introduced in the vacuum deposition method, so that the metal contained in the electron injection layer is oxidized. It can be avoided.
Hereinafter, each structure of such an organic EL element is demonstrated. The organic EL layer and the substrate are the same as those described in the first embodiment, and the electrode layer is the same as the first electrode layer described in the first embodiment. The description here is omitted.

(1) Semiconductor electrode layer First, the semiconductor electrode layer used for this embodiment is demonstrated. The semiconductor electrode layer used in this embodiment is formed on the organic EL layer and contains an inorganic compound and a metal having a band gap of 2.0 eV or more. The semiconductor electrode layer is formed as an electrode facing the electrode layer. The semiconductor electrode layer used in this embodiment may be an anode or a cathode, and may be transparent or translucent, or not transparent or translucent. For example, when extracting light from the semiconductor electrode layer side, the semiconductor electrode layer is required to be transparent or translucent. When extracting light from the substrate side, the semiconductor electrode layer may not be transparent or translucent. Good. Moreover, when taking out light from both sides of the base material side and the semiconductor electrode layer side, both the semiconductor electrode layer and the electrode layer are required to be transparent or translucent.

The semiconductor electrode layer used in this embodiment can be divided into four modes depending on the configuration of the semiconductor electrode layer. That is, when the semiconductor electrode layer is a mixed semiconductor layer in which a metal is dispersed in an inorganic compound (fifth aspect), the semiconductor electrode layer includes an inorganic layer made of an inorganic compound and a metal layer made of a metal. And when the metal layer is formed in the inorganic layer or on the surface opposite to the surface on which the organic EL layer is formed (sixth aspect), the semiconductor electrode layer is in the inorganic compound. When it has a mixed semiconductor layer in which a metal is dispersed and an inorganic layer made of an inorganic compound (seventh aspect), and the semiconductor electrode layer is made of a mixed semiconductor layer in which a metal is dispersed in an inorganic compound and a metal This is the case of having a metal layer (eighth aspect).
Hereinafter, each aspect of such a semiconductor electrode layer will be described.

(I) Fifth Aspect A fifth aspect of the semiconductor electrode layer used in the present embodiment is a mixed semiconductor layer in which a metal is dispersed in an inorganic compound.
Hereinafter, constituent materials of such a mixed semiconductor layer will be described.

(Inorganic compounds)
The inorganic compound used in this embodiment has a band gap of 2.0 eV or more. The inorganic compound used in this embodiment is not particularly limited as long as it can be a layer having a function as an electrode, and the above-mentioned “1. First embodiment (1) Semiconductor buffer layer”. The thing similar to what was described in the column of the 1st aspect can be used. In this embodiment, it is preferable to use at least one inorganic semiconductor compound selected from ZnS, ZnSe, GaN, and GaS.

(metal)
The metal used in this embodiment is not particularly limited as long as it can be a layer having a function as an electrode, but a metal that is difficult to be oxidized and has a work function of 4.0 eV or more is used. It is preferable. Examples of such metals include Ag, Al, Au, Be, Co, Cr, Cu, Ga, Fe, In, Ir, Mn, Mo, Nb, Ni, Os, Pb, Pt, Re, Ru, Sb, Sn, Ta, Ti, and W can be mentioned. These metals may be used independently and may use 2 or more types together. In this embodiment, it is preferable to use a metal having a work function of 4.2 eV or more, specifically, Ag, Al, Au, Be, Co, Cr, Cu, Ga, Fe, Ir, Mo, Nb. Ni, Os, Pb, Pt, Re, Ru, Sb, Sn, W and the like are preferably used.

  In addition, when the metal contained in the mixed semiconductor layer is a layer made of only a metal, the thickness of the layer made of only the metal is preferably 100 nm or less, among which 1 nm to 50 nm, more preferably 1 nm to 30 nm, In particular, it is preferably in the range of 1 nm to 20 nm. It is because the light transmittance of a mixed semiconductor layer may fall when the thickness of the layer which consists only of the said metal is too thick. On the contrary, if the thickness of the layer made of only the metal is too thin, the conductivity of the semiconductor buffer layer may be lowered. The thickness of the layer made of only the metal can be calculated by the method described in the first embodiment.

(Semiconductor electrode layer)
The thickness of the semiconductor electrode layer in this embodiment is not particularly limited as long as the thickness satisfies a predetermined average light transmittance and electrical resistivity, but is preferably in the range of 1 nm to 500 nm. In particular, it is preferably in the range of 10 nm to 200 nm, particularly 10 nm to 100 nm. This is because if the thickness of the semiconductor electrode layer is too thick, the light transmittance may decrease. Conversely, if the thickness of the semiconductor electrode layer is too thin, the function as an electrode may not be obtained.

  In addition, about the average light transmittance of a semiconductor electrode layer, an electrical resistivity, a formation method, etc., the semiconductor buffer layer described in the column of the 1st aspect of "1. First embodiment (1) Semiconductor buffer layer" mentioned above. The description thereof is omitted here.

(Ii) Sixth Aspect A sixth aspect of the semiconductor electrode layer used in this embodiment has an inorganic layer made of an inorganic compound and a metal layer made of a metal, and the metal layer is an inorganic layer. It is formed on the surface opposite to the surface on which the organic EL layer is formed.

  As the formation position of the inorganic layer and the metal layer in this embodiment, for example, as shown in FIG. 6, the metal layer 34b may be formed so as to be sandwiched between the inorganic layers 34a, and as shown in FIG. However, it may be formed on the surface opposite to the surface on which the organic EL layer 23 is formed, that is, formed on the inorganic layer 34a. Moreover, since the metal layer should just be the structure which does not contact | connect an organic EL layer, the some metal layer and the some inorganic layer may be laminated | stacked.

  In addition, the thickness of the metal layer in this embodiment is preferably 100 nm or less, more preferably 1 nm to 50 nm, more preferably 1 nm to 30 nm, and particularly preferably 1 nm to 20 nm. It is because the light transmittance of a semiconductor electrode layer may fall when the thickness of the said metal layer is too thick. Conversely, if the thickness of the metal layer is too thin, the conductivity of the semiconductor electrode layer may be lowered.

  The other points of the metal layer and the inorganic layer are the same as those described in the column of the second aspect of “1. First embodiment (1) Semiconductor buffer layer” described above. Since the average light transmittance and electrical resistivity of the electrode layer are the same as those of the semiconductor buffer layer described in the column of the first aspect of “1. First embodiment (1) Semiconductor buffer layer”, The description here is omitted. Furthermore, the thickness of the semiconductor electrode layer and the inorganic compound and metal that are preferably used are the same as in the fifth aspect.

(Iii) Seventh Aspect A seventh aspect of the semiconductor electrode layer used in this embodiment includes a mixed semiconductor layer in which a metal is dispersed in an inorganic compound and an inorganic layer made of an inorganic compound.

  The formation position of the mixed semiconductor layer and the inorganic layer in this embodiment is not particularly limited, and may be laminated in the order of the mixed semiconductor layer and the inorganic layer from the organic EL layer side. You may laminate | stack in order. A plurality of mixed semiconductor layers and inorganic layers may be stacked.

  The mixed semiconductor layer is the same as that described in the column of the first aspect of “1. First embodiment (1) Semiconductor buffer layer” described above, and the inorganic layer is described in “1. Since it is the same as that of what was described in the column of the 2nd aspect of "1st embodiment (1) Semiconductor buffer layer", description here is abbreviate | omitted. The average light transmittance, electrical resistivity, and the like of the semiconductor electrode layer are the same as those of the semiconductor buffer layer described in the column of the first aspect of “1. First embodiment (1) Semiconductor buffer layer” described above. Since it is the same, description here is abbreviate | omitted. Furthermore, the thickness of the semiconductor electrode layer and the inorganic compound and metal that are preferably used are the same as in the fifth aspect.

(Iv) Eighth Aspect The eighth aspect of the semiconductor electrode layer used in the present embodiment has a mixed semiconductor layer in which a metal is dispersed in an inorganic compound and a metal layer made of a metal.

  The formation position of the mixed semiconductor layer and the metal layer in this embodiment is not particularly limited, and the mixed semiconductor layer and the metal layer may be stacked in this order from the organic EL layer side. You may laminate | stack in order. A plurality of mixed semiconductor layers and metal layers may be stacked.

  The mixed semiconductor layer is the same as that described in the column of the first aspect of “1. First embodiment (1) Semiconductor buffer layer” described above, and the metal layer is described in “1. First Embodiment (1) The same as that described in the column of the fourth embodiment of “Semiconductor Buffer Layer”, and the light transmittance and electrical resistivity of the semiconductor electrode layer are described in “1. First Embodiment”. Since it is the same as that of the semiconductor buffer layer described in the column of the first aspect of “Aspect (1) Semiconductor Buffer Layer”, description thereof is omitted here. Furthermore, the thickness of the semiconductor electrode layer, the thickness of the metal layer, and the inorganic compound and metal that are preferably used are the same as in the fifth aspect.

(V) Others In addition to the configuration described above, the semiconductor electrode layer in the present embodiment may be a stacked layer of a mixed semiconductor layer, a metal layer, and an inorganic layer. In this case, the formation position of the mixed semiconductor layer, the metal layer, and the inorganic layer is not particularly limited. For example, a layer in which a mixed semiconductor layer, a metal layer, and an inorganic layer are stacked in this order from the organic EL layer side, a layer in which an inorganic layer, a mixed semiconductor layer, and a metal layer are stacked in this order can be used.

(6) Charge Injecting and Transporting Layer In this embodiment, for example, as shown in FIG. 8, between the light emitting layer and the electrode layer 22 in the organic EL layer 23 or the light emitting layer and the semiconductor in the organic EL layer 23. A charge injection / transport layer 26 may be formed between the electrode layer 24 and the electrode layer 24. The charge injecting and transporting layer has a function of stably transporting charges from the electrode layer or the semiconductor electrode layer to the light emitting layer, and the charge injecting and transporting layer is used between the light emitting layer and the electrode layer or emitting light. By providing between the layer and the semiconductor electrode layer, the injection of charge into the light emitting layer is stabilized, and the light emission efficiency can be increased.

  The charge injecting and transporting layer is the same as that described in the first embodiment described above, and the description thereof is omitted here.

  In this embodiment, depending on the above-described aspects of the semiconductor electrode layer (fifth to eighth aspects), the type of metal contained in the semiconductor electrode layer, and the type of semiconductor electrode layer (anode, cathode), It may be preferable to form a charge injecting and transporting layer. Hereinafter, each aspect of the semiconductor electrode layer will be described.

(When the semiconductor electrode layer is the fifth aspect)
This embodiment is a case where the semiconductor electrode layer is a mixed semiconductor layer.
In this embodiment, when the semiconductor electrode layer is a cathode and the work function of the metal contained in the mixed semiconductor layer, which is the semiconductor electrode layer, is 4.0 eV or more, electrons are interposed between the mixed semiconductor layer and the light emitting layer. It is preferable to provide an injection transport layer. If the value of the work function of the metal is large, the energy barrier at the interface between the mixed semiconductor layer and the light emitting layer increases, and it may be difficult to inject electrons directly from the mixed semiconductor layer to the light emitting layer under a low voltage. However, by providing an electron injecting and transporting layer between the mixed semiconductor layer and the light emitting layer, electrons can be efficiently injected into the light emitting layer. At this time, when extracting light from the mixed semiconductor layer side, the electron injecting and transporting layer preferably has sufficient light transmittance.

  Furthermore, when the semiconductor electrode layer is an anode and the work function of the metal contained in the mixed semiconductor layer that is the semiconductor electrode layer is 4.0 eV or more, hole injection is performed between the mixed semiconductor layer and the light emitting layer. A transport layer may not be provided. This is because, since the work function value of the metal is large, holes can be stably injected into the light emitting layer.

(When the semiconductor electrode layer is the sixth aspect)
This embodiment is a case where the semiconductor electrode layer has an inorganic layer and a metal layer. In this embodiment, it is preferable to provide a charge injecting and transporting layer between the light emitting layer and the semiconductor electrode layer. In this case, since the metal layer is formed so as not to be in contact with the organic EL layer, there is a possibility that charge injection may be insufficient. However, a charge injection / transport layer is provided between the light emitting layer and the semiconductor electrode layer. This is because charges can be efficiently injected into the light emitting layer. At this time, when taking out light from the semiconductor electrode layer side, the charge injecting and transporting layer preferably has sufficient light transmittance.

(When the semiconductor electrode layer is the seventh aspect)
This embodiment is a case where the semiconductor electrode layer has a mixed semiconductor layer and an inorganic layer.
In this embodiment, when the inorganic layer is formed so as to be in contact with the organic EL layer, it is preferable to provide a charge injecting and transporting layer between the light emitting layer and the inorganic layer. In this case, since the metal contained in the mixed semiconductor layer is not in contact with the organic EL layer, there is a possibility that charge injection is insufficient, but a charge injection / transport layer is provided between the light emitting layer and the inorganic layer. This is because charges can be efficiently injected into the light emitting layer. At this time, when taking out light from the semiconductor electrode layer side, the charge injecting and transporting layer preferably has sufficient light transmittance.

  Furthermore, in this embodiment, the mixed semiconductor layer is formed so as to be in contact with the organic EL layer, the semiconductor electrode layer is the anode, and the work function of the metal contained in the mixed semiconductor layer is 4.0 eV. In the above case, it is not necessary to provide a hole injecting and transporting layer between the mixed semiconductor layer and the light emitting layer. This is because, since the work function value of the metal is large, holes can be stably injected into the light emitting layer.

(When the semiconductor slow electrode layer is the eighth aspect)
This embodiment is a case where the semiconductor electrode layer has a mixed semiconductor layer and a metal layer.
In this embodiment, when the semiconductor electrode layer is an anode and the work function of the metal contained in the layer in contact with the organic EL layer of the mixed semiconductor layer and the metal layer is 4.0 eV or more, the semiconductor electrode It is not necessary to provide a hole injecting and transporting layer between the layer and the light emitting layer. This is because, since the work function value of the metal is large, holes can be stably injected into the light emitting layer.

  Since the other points of the organic EL element are the same as those described in the first embodiment, description thereof is omitted here.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be specifically described using examples and comparative examples.

[Example 1]
(Formation of first electrode layer)
As a base material, a transparent glass substrate (non-alkali glass NA35 manufactured by NH Techno Glass Co., Ltd.) having a size of 40 mm × 40 mm and a thickness of 0.7 mm was prepared. A thin film (thickness 130 nm) of indium zinc oxide compound (IZO) was formed as an anode on the substrate by a sputtering method. When forming the IZO thin film, a mixed gas of Ar and O ₂ (volume ratio Ar: O ₂ = 100: 1) was used as the sputtering gas, and the pressure was 0.1 Pa and the DC output was 150 W. Furthermore, a photosensitive resist (OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied onto the IZO thin film (anode), mask exposure, development (using NMD3 manufactured by Tokyo Ohka Kogyo Co., Ltd.), and etching are performed. The IZO thin film (anode) was patterned.

(Formation of hole injection transport layer)
The transparent glass substrate provided with the IZO thin film (anode) is washed, subjected to UV ozone treatment, and then expressed in the following chemical formula (1) on the transparent glass substrate so as to cover the IZO thin film (anode) in the air. Polyethylene dioxythiophene-polystyrene sulfonate (PEDOT-PSS) was applied by spin coating and dried to form a hole injection transport layer (thickness 80 nm).

  Here, in Formula (1), n is 10,000-500,000.

(Formation of light emitting layer)
Poly (9,9 dioctylfluorene-co represented by the following chemical formula (2) on the hole injecting and transporting layer in a low oxygen (oxygen concentration 1 ppm or less) and low humidity (water vapor concentration 1 ppm or less) glove box. -A polymer (5BTF8) composed of benzothiazole) (F8BT) and poly (9,9 dioctylfluorene) (PF8) was applied by spin coating and dried to form a light emitting layer (thickness 80 nm). The polymer (5BTF8) is a light emitting material in which F8BT and PF8 are blended at a weight ratio of 5:95.

  Here, in Formula (2), n is 100,000-1,000,000.

(Formation of electron injection layer)
Ca was vapor-deposited with a thickness of 3 nm on the light emitting layer to form an electron injection layer. The deposition conditions were a degree of vacuum of 5 × 10 ⁻⁵ Pa and a film formation rate of 1 kg / second.

(Formation of semiconductor buffer layer)
ZnSe and Ca were co-evaporated on the electron injection layer to form a semiconductor buffer layer having a thickness of 30 nm. The deposition conditions were a volume ratio of ZnSe and Ca of 10: 1, a degree of vacuum of 5 × 10 ⁻⁵ Pa, a ZnSe film formation rate of 1 Å / second, and a Ca film formation rate of 0.1 Å / second.

(Formation of second electrode layer)
Further, an IZO thin film (thickness: 100 nm) was formed on the semiconductor buffer layer by a counter target sputtering method to form a cathode. When forming the IZO thin film, Ar was used as the sputtering gas, and the pressure was 7.0 × 10 ⁻² Pa, the DC output was 150 W, and the RF output was 100 W.

(Production of organic EL element)
After forming the second electrode layer, sealing was performed with alkali-free glass in a glove box in a low oxygen (oxygen concentration 1 ppm or less) and low humidity (water vapor concentration 1 ppm or less) state. By the series of operations described above, an anode patterned into a line shape with a width of 2 mm, and an electron injection layer, a semiconductor buffer layer, and a cathode patterned into a line shape with a width of 2 mm so as to be orthogonal to the pattern of the anode, An organic EL element having four light emitting areas (area 4 mm ² ) was produced.

The current density when a voltage of 6 V was applied to the anode and cathode of this organic EL element was about 215 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (cathode) side was about 4000 cd / m ² . From this result, in the light emitting area, the presence of the semiconductor buffer layer, which is a mixed semiconductor layer of ZnSe and Ca, prevents the light emitting layer and the electron injection layer from being oxidized during sputtering and damage caused by sputtering. confirmed.

(Evaluation of light transmittance and resistivity)
In addition, an electron injection layer, a semiconductor buffer layer, and a second electrode layer were sequentially formed on the transparent glass substrate by the above-described forming method, and a laminate was manufactured. About this laminated body, the specific resistance value and the light transmittance in visible region 380-780 nm were measured on condition of the following. As a result, the average light transmittance in the visible region was about 60%, and the light transmittance at a wavelength of 500 nm was about 70%. Moreover, the average specific resistance value of the laminate (thickness 130 nm) was 8 × 10 ⁻³ Ω · cm.

<Measurement of film thickness>
The film thickness was measured using Nanopics 1000 manufactured by Seiko Instruments Inc.

<Measurement of light transmittance>
It measured in room temperature and air | atmosphere using the ultraviolet visible spectrophotometer (Shimadzu Corporation UV-2200A).

<Measurement of specific resistance value>
The specific resistance value was measured by a four-probe method using Dia Instruments Loresta-GP (MCP-T600).

[Example 2]
An organic EL device was produced in the same manner as in Example 1 except that ZnS and Ca were co-evaporated as a semiconductor buffer layer to form a semiconductor buffer layer having a thickness of 30 nm. The deposition conditions for forming the semiconductor buffer layer are as follows: the volume ratio of ZnS and Ca is 10: 1, the degree of vacuum is 5 × 10 ⁻⁵ Pa, the deposition rate of ZnS is 1 Å / sec, the deposition rate of Ca is 0. It was 1 liter / second.

The current density when a voltage of 6 V was applied to the anode and cathode of the organic EL element was about 230 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (cathode) side was about 4500 cd / m ² . From this result, it was confirmed that the presence of the semiconductor buffer layer, which is a mixed semiconductor layer of ZnS and Ca, prevents the light emitting layer and the electron injection layer from being oxidized and damaged during sputtering during the cathode formation.

[Example 3]
(Formation of first electrode layer)
As a base material, a transparent glass substrate (non-alkali glass NA35 manufactured by NH Techno Glass Co., Ltd.) having a size of 40 mm × 40 mm and a thickness of 0.7 mm was prepared. A thin film made of chromium having a thickness of 150 nm was formed on the substrate as an anode by a magnetron sputtering method. When the chromium thin film was formed, Ar was used as the sputtering gas, the pressure was 0.3 Pa, and the DC output was 200 W. Then, patterning of a chromium thin film (anode) by a photolithography method (resist: OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd., etching solution: Cr-01N manufactured by Kanto Chemical Co., Ltd.) to form a pattern of 2 mm wide lines × 2 lines Went.

Furthermore, the plasma processing of the transparent glass substrate provided with the said chromium thin film (anode) was performed. First, Ar was used as the sputtering gas, the pressure was set to 1.0 Pa, and the RF output was set to 100 W. After removing the oxide layer on the surface of the chromium thin film that has been naturally oxidized, plasma treatment is performed using Ar and O ₂ as sputtering gases, gas partial pressure Ar: O ₂ = 1: 1, pressure 1.0 Pa, RF output 100 W for 1 minute. Went.

(Formation of hole injection transport layer, light emitting layer, electron injection layer, and semiconductor buffer layer)
In the same manner as in Example 1, a hole injection transport layer, a light emitting layer, an electron injection layer, and a semiconductor buffer layer were sequentially formed on the chromium thin film (anode).

(Formation of second electrode layer)
Further, an IZO thin film (thickness: 100 nm) was formed on the semiconductor buffer layer by a counter target sputtering method to form a cathode. When forming the IZO thin film, Ar was used as the sputtering gas, the pressure was 0.07 Pa, the RF output was 100 W, and the DC output was 5 W.

(Production of organic EL element)
Sealing was performed in the same manner as in Example 1 to produce an organic EL element.
Current density when the voltage 6V is applied to the anode and the cathode of the organic EL element is about 220 mA / cm ^2, the luminance of the light emitting area measured from the upper surface (cathode) side was about 9000 cd / ^{m 2.} From this result, it was confirmed that the presence of the semiconductor buffer layer, which is a mixed semiconductor layer of ZnSe and Ca, prevented the oxidation of the light emitting layer and the electron injection layer during the formation of the cathode and damage during sputtering.

[Comparative Example 1]
An organic EL device was produced in the same manner as in Example 1 except that the semiconductor buffer layer was not formed and an IZO thin film was formed as a cathode on the electron injection layer.

The current density when a voltage of 6 V is applied to the anode and cathode of the organic EL display element is about 0.18 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (cathode) side is about 0.2 cd / m. ² . From this result, it was confirmed that in the organic EL element in which the semiconductor buffer layer was not formed, the light emission characteristics were deteriorated due to the oxidation of the electron injection layer by oxygen at the time of forming the cathode.

[Comparative Example 2]
An organic EL element was produced in the same manner as in Example 1 except that a 30 nm semiconductor buffer layer was formed using only ZnSe as the semiconductor buffer layer.

The current density when a voltage of 6 V was applied to the anode and cathode of the organic EL element was about 19 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (cathode) side was about 1000 cd / m ² . From this result, it was confirmed that in the organic EL element in which the metal is not contained in the semiconductor buffer layer, the charge transport function in the semiconductor buffer layer is lowered and the light emission characteristics are lowered.

[Comparative Example 3]
An organic EL element was produced in the same manner as in Example 1 except that a 30 nm semiconductor buffer layer was formed using only ZnS as the semiconductor buffer layer.

The current density when a voltage of 6 V was applied to the anode and cathode of the organic EL element was about 50 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (cathode) side was about 1480 cd / m ² . From this result, it was confirmed that in the organic EL element in which the metal is not contained in the semiconductor buffer layer, the charge transport function in the semiconductor buffer layer is lowered and the light emission characteristics are lowered.

[Example 4]
(Formation of first electrode layer)
In the same manner as in Example 1, an IZO thin film was formed as an anode on a transparent glass substrate.

(Formation of hole injection layer and hole transport layer)
The transparent glass substrate provided with the IZO thin film (anode) is exposed to oxygen plasma, and then the tris represented by the following chemical formula (3) on the transparent glass substrate so as to cover the IZO thin film (anode) by vacuum heating deposition. A hole injection layer (thickness 30 nm) made of [naphthyl (phenyl) amino] triphenylamine (1-TNATA) was formed. The film formation conditions for this hole injection layer were as follows: the degree of vacuum was 5 × 10 ⁻⁵ Pa, the film formation rate was 2 kg / second, and the heating temperature was 350 ° C.

Furthermore, a hole transport layer (thickness 30 nm) made of bis (N-naphthyl) -N-phenylbenzidine (α-NPD) represented by the following chemical formula (4) is formed on the hole injection layer by a vacuum deposition method. did. The film formation conditions for this hole transport layer were a degree of vacuum of 5 × 10 ⁻⁵ Pa, a film formation rate of 2 kg / second, and a heating temperature of 350 ° C.

(Formation of light emitting layer)
On the hole transport layer, a tris (8-quinolinolato) aluminum complex (Alq3) represented by the following chemical formula (5) and a coumarin 6 (C6) represented by the following chemical formula (6) were formed by co-evaporation. A light emitting layer (thickness 40 nm) was formed. The film forming conditions of the light emitting layer were that Alq3 was doped with C6 so that C6 was in a weight ratio of 1%, the degree of vacuum was 5 × 10 ⁻⁵ Pa, and the film forming rate of Alq3 was 2 Å / sec.

(Formation of electron transport layer and electron injection layer)
On the light emitting layer, an electron transport layer (thickness 20 nm) made of bathocuproine (BCP) represented by the following chemical formula (7) was formed by vacuum deposition. The electron transport layer was formed under the conditions of a degree of vacuum of 5 × 10 ⁻⁵ Pa and a film formation rate of 2 L / second.

Furthermore, an electron injection layer (thickness 3 nm) made of Li was formed on the electron transport layer by a vacuum deposition method. The film formation conditions for the electron injection layer were a vacuum degree of 5 × 10 ⁻⁵ Pa and a film formation rate of 0.2 kg / sec.

(Formation of semiconductor buffer layer and second electrode layer)
In the same manner as in Example 2, a semiconductor buffer layer and a second electrode layer were formed, sealed, and an organic EL element was produced.

The current density when a voltage of 6 V was applied to the anode and cathode of this organic EL element was about 150 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (cathode) side was about 3300 cd / m ² . From this result, it is confirmed that the presence of the semiconductor buffer layer, which is a mixed semiconductor layer of ZnS and Ca, prevents oxidation of the electron injection layer during cathode formation and damage to the light emitting layer and electron injection layer during sputtering. It was done.

[Example 5]
(Formation of first electrode layer)
In the same manner as in Example 1, an IZO thin film was formed as a cathode on a transparent glass substrate.

(Formation of electron injection layer and electron transport layer)
The transparent glass substrate provided with the IZO thin film (cathode) is exposed to argon plasma, and then BCP and Li are co-deposited on the transparent glass substrate so as to cover the IZO thin film (cathode) by vacuum heating vapor deposition. An electron injection layer (thickness 20 nm) was formed. The electron injection layer was formed by co-evaporation so that the degree of vacuum was 5 × 10 ⁻⁵ Pa, the BCP film formation rate was 2 Å / sec, and the molar ratio of BCP and Li was 1: 2.

  Further, in the same manner as in Example 4, an electron transport layer (thickness 20 nm) made of BCP was formed on the electron injection layer.

(Formation of light emitting layer)
In the same manner as in Example 4, a light emitting layer (thickness 40 nm) made of Alq3 and C6 was formed on the electron transport layer.

(Formation of hole transport layer and hole injection layer)
In the same manner as in Example 4, a hole transport layer (thickness 30 nm) made of α-NPD and a hole injection layer (thickness 30 nm) made of 1-TNATA were sequentially formed on the light emitting layer.

(Formation of semiconductor buffer layer)
On the hole injection layer, ZnS and Au were co-evaporated to form a 30 nm-thick semiconductor buffer layer. The film formation conditions of this semiconductor buffer layer are as follows: the volume ratio of ZnS and Au is 10: 1, the degree of vacuum is 5 × 10 ⁻⁵ Pa, the film formation speed of ZnS is 1 Å / second, and the film formation speed of Au is 0.1 Å / second. It was.

(Formation of second electrode layer)
On the semiconductor buffer layer, an IZO thin film (thickness: 100 nm) was formed as an anode and sealed to produce an organic EL element.

The current density when a voltage of 6 V was applied to the anode and cathode of this organic EL element was about 101 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (anode) side was about 2800 cd / m ² . From this result, it is confirmed that the presence of the semiconductor buffer layer, which is a mixed semiconductor layer of ZnS and Au, prevents the light emitting layer, the hole transport layer, and the hole injection layer from being damaged during sputtering during anode formation. It was done.

[Comparative Example 4]
An organic EL element was produced in the same manner as in Example 4 except that the IZO thin film was formed as a cathode on the electron injection layer without forming the semiconductor buffer layer.

The current density when a voltage of 6 V is applied to the anode and cathode of the organic EL element is about 1.2 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (cathode) side is about 4.6 cd / m ^2. Met. From this result, it was confirmed that the organic EL device without the semiconductor buffer layer has a large leakage current due to oxidation of the electron injection layer during cathode formation and damage to the light emitting layer and electron transport layer due to sputtering, resulting in a decrease in light emission characteristics. It was done.

[Comparative Example 5]
An organic EL element was produced in the same manner as in Example 4 except that a semiconductor buffer layer (thickness 30 nm) made of only ZnS was formed as the semiconductor buffer layer.

The current density when a voltage of 6 V was applied to the anode and cathode of the organic EL element was about 80 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (cathode) side was about 4100 cd / m ² . From this result, it was confirmed that in the organic EL element in which the metal is not contained in the semiconductor buffer layer, the charge transport function in the semiconductor buffer layer is lowered and the light emission characteristics are lowered.

[Example 6]
As a semiconductor buffer layer, ZnS is vapor-deposited to a thickness of 30 nm, then Au is vapor-deposited to a thickness of 5 nm, and further ZnS is vapor-deposited to a thickness of 30 nm to form an inorganic layer (ZnS), a metal layer ( An organic EL element was produced in the same manner as in Example 1 except that a semiconductor buffer layer composed of Au) and an inorganic layer (ZnS) was formed.

The current density when a voltage of 6 V was applied to the anode and cathode of this organic EL element was about 190 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (cathode) side was about 4000 cd / m ² . From this result, it was confirmed that the presence of the semiconductor buffer layer having a laminated structure of ZnS / Au / ZnS prevented the oxidation of the light emitting layer and the electron injection layer during the formation of the cathode and the damage during the sputtering.

[Example 7]
In the same manner as in Example 1, an IZO thin film (cathode), a hole injection transport layer, a light emitting layer, and an electron injection layer were sequentially formed on a transparent glass substrate. Thereafter, ZnSe and Au were co-evaporated on the electron injection layer to form a semiconductor electrode layer (anode) having a thickness of 100 nm, and an organic EL element was produced. The deposition conditions of the semiconductor electrode layer are as follows: the volume ratio of ZnSe and Au is 10: 1, the degree of vacuum is 5 × 10 ⁻⁵ Pa, the deposition rate of ZnSe is 1 Å / sec, and the deposition rate of Au is 0.1 Å / sec. did.

The current density when a voltage of 6 V was applied to the anode and cathode of this organic EL element was about 210 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (cathode) side was about 4300 cd / m ² . From this result, by forming a semiconductor electrode layer that is a mixed semiconductor layer of ZnSe and Au, an anode can be formed without performing sputtering, so that damage to the light emitting layer and the electron injection layer during oxidation and sputtering can be avoided. It was confirmed that good characteristics were obtained.

[Example 8]
An organic EL device was produced in the same manner as in Example 1 except that CaF ₂ and Au were co-evaporated as a semiconductor buffer layer to form a 30 nm-thick semiconductor buffer layer. Deposition conditions were such that the volume ratio of CaF ₂ and Au was 2: 1, the degree of vacuum was 5 × 10 ⁻⁵ Pa, the deposition rate of CaF ₂ was 1 Å / sec, and the deposition rate of Au was 0.5 Å / sec. Here, the light transmittance of only the semiconductor buffer layer having a thickness of 30 nm was about 65% at a wavelength of 510 nm.

The current density when a voltage of 6 V was applied to the anode and cathode of this organic EL element was about 190 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (cathode) side was about 3500 cd / m ² . From this result, it was confirmed that the presence of the semiconductor buffer layer, which is a mixed semiconductor layer of CaF ₂ and Au, prevents the light emitting layer and the electron injection layer from being oxidized and damaged during sputtering when the cathode is formed.

[Example 9]
In the same manner as in Example 1, an anode, a hole injection transport layer, a light emitting layer, and an electron injection layer were formed on a transparent glass substrate. This electron injection layer by co-evaporation CaF ₂ and Au, the formation of the semiconductor electrode layer having a thickness of 50nm. Deposition conditions were such that the volume ratio of CaF ₂ and Au was 2: 1, the degree of vacuum was 5 × 10 ⁻⁵ Pa, the deposition rate of CaF ₂ was 1 Å / sec, and the deposition rate of Au was 0.5 Å / sec. Here, the light transmittance of only the semiconductor electrode layer having a thickness of 50 nm was about 52% at a wavelength of 510 nm.

The current density when a voltage of 6 V was applied to the anode and cathode of this organic EL element was about 160 mA / cm ² , and the luminance of the light emitting area measured from the upper surface (cathode) side was about 3000 cd / m ² . From this result, by forming a semiconductor electrode layer, which is a mixed semiconductor layer of CaF ₂ and Au, using a vacuum deposition method, a cathode can be formed without damaging the light emitting layer, and an electron injection layer can be formed. It was confirmed that the oxidation of was prevented.

DESCRIPTION OF SYMBOLS 1, 21 ... Base material 2 ... 1st electrode layer 3, 23 ... Organic EL layer 4 ... Semiconductor buffer layer 5 ... 2nd electrode layer 6, 26 ... Charge injection transport layer 14a, 34a ... Inorganic layer 14b, 34b ... Metal layer 22 ... Electrode layer 24 ... Semiconductor electrode layer

Claims (16)

  A base material, an electrode layer formed on the base material, an organic electroluminescent layer formed on the electrode layer and having at least a light emitting layer, and formed on the organic electroluminescent layer, with a band gap of 2 An organic electroluminescent device comprising: a semiconductor electrode layer containing an inorganic compound and a metal of 0.0 eV or more.   The organic electroluminescence device according to claim 1, wherein the semiconductor electrode layer is a mixed semiconductor layer in which the metal is dispersed in the inorganic compound.   The semiconductor electrode layer has an inorganic layer made of the inorganic compound and a metal layer made of the metal, and the metal layer is opposite to the surface in which the organic electroluminescent layer is formed or in the inorganic layer. The organic electroluminescence device according to claim 1, wherein the organic electroluminescence device is formed on a surface.   2. The organic electroluminescence device according to claim 1, wherein the semiconductor electrode layer includes a mixed semiconductor layer in which the metal is dispersed in the inorganic compound and an inorganic layer made of the inorganic compound.   2. The organic electroluminescence device according to claim 1, wherein the semiconductor electrode layer includes a mixed semiconductor layer in which the metal is dispersed in the inorganic compound and a metal layer made of the metal. A substrate, a first electrode layer formed on the substrate, an organic electroluminescence layer formed on the first electrode layer and having at least a light emitting layer, and formed on the organic electroluminescence layer, A semiconductor buffer layer containing an inorganic compound and a metal having a band gap of 2.0 eV or more, and a second electrode layer formed on the semiconductor buffer layer;
The semiconductor buffer layer has an inorganic layer made of the inorganic compound and a metal layer made of the metal, and the metal layer is formed in the inorganic layer or between the inorganic layer and the second electrode layer. An organic electroluminescence device characterized by being made. The organic electroluminescence element according to claim 1, wherein the metal has an electrical resistivity ρ of less than 1 × 10 ⁻⁵ Ω · cm.   8. The organic electroluminescence according to claim 1, wherein a work function of a metal contained in the semiconductor electrode layer is 4.2 eV or more, or the organic electroluminescence according to claim 7. element.   The organic electroluminescent element according to any one of claims 1 to 8, wherein the inorganic compound is an inorganic semiconductor compound.   10. The organic electro luminescent device according to claim 9, wherein the inorganic semiconductor compound is a compound containing at least one element selected from elements of group 12 to group 16 of the group 18 element periodic table. Luminescence element.   The said inorganic compound is a metal compound containing the at least 1 sort (s) of element selected from the group 17 element of a group 18 type | mold element periodic table, The claim 1, 2, 5, The organic electroluminescent element according to claim 7 or 8.   The semiconductor buffer layer or the semiconductor electrode layer has a thickness in a range of 1 nm to 500 nm, and an average light transmittance in a visible region of 30% or more. An organic electroluminescence device according to any one of the claims.   The content of the metal in the semiconductor buffer layer or the semiconductor electrode layer is in a range of 0.0001% by volume to 90% by volume, according to any one of claims 1 to 12. The organic electroluminescent element according to claim.   When the metal contained in the semiconductor buffer layer or the semiconductor electrode layer is a layer made of only a metal, the semiconductor buffer layer has a thickness of 100 nm or less. Or it contains in the said semiconductor electrode layer, The organic electroluminescent element in any one of Claim 1-13 characterized by the above-mentioned.   The organic electroluminescence element according to any one of claims 1 to 14, wherein the semiconductor buffer layer or the semiconductor electrode layer is formed by a vacuum deposition method.   16. The organic material according to claim 1, wherein a charge injecting and transporting layer is formed between the light emitting layer and the semiconductor buffer layer or the semiconductor electrode layer. Electroluminescence element.

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