WO2014175181A1

WO2014175181A1 - Transparent conductor and electronic device

Info

Publication number: WO2014175181A1
Application number: PCT/JP2014/061049
Authority: WO
Inventors: 健波木井; 敏幸木下; 小島　茂; 和央吉田
Original assignee: コニカミノルタ株式会社
Priority date: 2013-04-22
Filing date: 2014-04-18
Publication date: 2014-10-30
Also published as: JPWO2014175181A1

Abstract

This transparent conductor is configured by being provided with an organic compound layer, and a conductive layer that is provided adjacent to the organic compound layer. In the transparent conductor, the conductive layer is configured from a metal layer having silver (Ag) as a main component, and a palladium-containing layer that contains palladium (Pd), said palladium-containing layer being provided on the organic compound layer side of the conductive layer.

Description

Transparent conductor and electronic device

The present invention relates to a transparent conductor and an electronic device including the transparent conductor.

An organic electroluminescence device (so-called organic EL device) using electroluminescence (hereinafter referred to as EL) of an organic material is a thin-film type completely solid device capable of emitting light at a low voltage of several V to several tens V. It has many excellent features such as high brightness, high luminous efficiency, thinness, and light weight. For this reason, it has been attracting attention in recent years as surface light emitters such as backlights for various displays, display boards such as signboards and emergency lights, and illumination light sources.

Such an organic electroluminescent element has a configuration in which a light emitting layer composed of an organic material is sandwiched between two electrodes, and emitted light generated in the light emitting layer passes through the electrode and is extracted outside. For this reason, at least one of the two electrodes is configured as a transparent conductor.

As the transparent conductor, oxide semiconductor materials such as indium tin oxide (ITO) and materials aiming at low resistance by laminating ITO and silver have been studied (for example, the following) (See Patent Document 1 and Patent Document 2). However, since ITO uses rare metal indium, the material cost is high, and it is necessary to anneal at about 300 ° C. after formation in order to reduce resistance. Then, the structure which ensures electroconductivity by the thickness thinner than silver alone by mixing aluminum with silver is also proposed (for example, refer patent document 3 below).

JP 2002-15623 A JP 2006-16961 A JP 2009-151963 A

However, even with a transparent conductor composed of silver and aluminum, it has been difficult to achieve both sufficient conductivity and light transmittance.

Therefore, the present invention provides a transparent conductor having both sufficient conductivity and light transmittance, and an electronic device whose performance is improved by using this transparent conductor.

The transparent conductor of the present invention includes an organic compound layer and a conductive layer provided adjacent to the organic compound layer. The conductive layer includes a metal layer containing silver (Ag) as a main component and a palladium-containing layer containing palladium (Pd), and the palladium-containing layer is provided on the organic compound layer side in the conductive layer.
Moreover, the electronic device of this invention is equipped with the said transparent conductor.

According to the transparent conductor of the present invention, since it has a conductive layer in which a metal layer mainly composed of silver is formed adjacent to the palladium-containing layer, interaction between palladium and silver is obtained, and although it is thin, it is uniform A conductive layer having a sufficient thickness can be obtained. Furthermore, the uniformity of the conductive layer can be further improved by providing the conductive layer on the organic compound layer.
Therefore, in the transparent conductor, it is possible to achieve both improvement in conductivity and improvement in light transmittance. Moreover, the electronic device excellent in electroconductivity and light transmittance can be comprised using this transparent conductor.

According to the present invention, it is possible to provide a transparent conductor and an electronic device that are excellent in conductivity and light transmittance.

It is a figure which shows schematic structure of the transparent conductor of 1st Embodiment. It is a figure which shows the structural formula of TBAC and Ir (ppy) ₃ for demonstrating the coupling | bonding mode of a nitrogen atom. It is a figure which shows the structural formula and molecular orbital of a pyridine ring. It is a figure which shows the structural formula and molecular orbital of a pyrrole ring. It is a figure which shows the structural formula and molecular orbital of an imidazole ring. FIG. 2 is a diagram showing a structural formula and molecular orbital of a δ-carboline ring. It is a figure which shows schematic structure of the transparent conductor of 2nd Embodiment. It is a figure which shows the admittance locus | trajectory at the time of forming a conductive layer on a base material. It is a figure which shows the admittance locus | trajectory of the transparent conductor of 2nd Embodiment. It is a figure which shows schematic structure of the transparent conductor of 3rd Embodiment. It is a figure which shows the admittance locus | trajectory of the transparent conductor of 3rd Embodiment. It is a figure which shows schematic structure of the organic electroluminescent element of 4th Embodiment. 3 is a diagram showing a schematic configuration of a bottom emission type organic electroluminescence device produced in Example 2. FIG.

Examples of the best mode for carrying out the present invention will be described below, but the present invention is not limited to the following examples.
The description will be given in the following order.
1. Transparent conductor (first embodiment)
2. Transparent conductor (second embodiment)
3. Transparent conductor (third embodiment)
4). Organic electroluminescent device (fourth embodiment)
5. Lighting device (fifth embodiment)

<1. Transparent conductor (first embodiment)>
A first embodiment of the present invention will be described. In FIG. 1, the schematic block diagram (sectional drawing) of the transparent conductor of 1st Embodiment is shown.

[Configuration of transparent conductor]
As shown in FIG. 1, the transparent conductor 10 includes an organic compound layer 12 and a conductive layer 15. The conductive layer 15 includes a metal layer 14 and a palladium-containing layer 13 adjacent to the metal layer 14. The palladium-containing layer 13 is provided on the organic compound layer 12 side in the conductive layer 15. That is, the palladium-containing layer 13 is sandwiched between the metal layer 14 and the organic compound layer 12. A transparent conductor 10 including an organic compound layer 12 and a conductive layer 15 composed of a palladium-containing layer 13 and a metal layer 14 is provided on the substrate 11.
Therefore, the transparent conductor 10 has a configuration in which the organic compound layer 12, the palladium-containing layer 13, and the metal layer 14 are laminated on the base material 11 in this order. The palladium-containing layer 13 of the conductive layer 15 is sandwiched between the organic compound layer 12 and the metal layer 14.

The transparent conductor 10 preferably has an average absorptance of light with a wavelength of 400 nm to 800 nm of 15% or less and a maximum absorptance of 25% or less.
The transparent conductor 10 has an average absorptance of light having a wavelength of 400 nm to 800 nm of 15% or less, preferably 12% or less, and more preferably 10% or less. Further, the maximum value of the absorptance of light having a wavelength of 400 nm to 800 nm is 25% or less, preferably 20% or less, and more preferably 15% or less. The light absorption rate of the transparent conductor 10 can be reduced by suppressing the plasmon absorption rate of the conductive layer 15 and the light absorption rate of the material constituting each layer.

The average transmittance of light having a wavelength of 450 nm to 800 nm of the transparent conductor 10 is preferably 50% or more, more preferably 70% or more, and further preferably 80% or more. On the other hand, the average reflectance of light having a wavelength of 500 nm to 700 nm of the transparent conductor 10 is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. The transparent conductor 10 is applicable also to the use as which high transparency is requested | required as the average transmittance | permeability of the light of the said wavelength is 50% or more and average reflectance 20% or less.

The absorptance, average transmittance, and average reflectance are values measured by allowing measurement light to enter the transparent conductor from an angle inclined by 5 ° with respect to the front surface of the transparent conductor. Absorptivity, average transmittance and average reflectance are measured with a spectrophotometer.

The surface resistance of the transparent conductor 10 is 30Ω / sq. Or less, more preferably 15 Ω / sq. It is as follows. The surface resistance value of the transparent conductor 10 can be adjusted by the thickness of the conductive layer 15 and the like. The surface resistance value of the transparent conductor 10 can be measured according to, for example, JIS K7194, ASTM D257, and the like. It can also be measured by a commercially available surface resistivity meter.

Hereinafter, the detailed structure of the transparent conductor 10 of this example will be described in the order of the substrate 11, the organic compound layer 12, and the conductive layer 15. In the transparent conductor 10 of this example, “transparent” means that the light transmittance at a wavelength of 550 nm is 50% or more.

[Substrate 11]
The base material 11 on which the transparent conductor 10 is formed is a support material for various elements formed thereon. The substrate 11 is preferably highly transparent to visible light. Examples of the substrate 11 include, but are not limited to, glass, quartz, a transparent resin film, and the like.

The base material 11 preferably has an average transmittance of light having a wavelength of 450 to 800 nm of 70% or more, more preferably 80% or more, and further preferably 85% or more. When the average light transmittance of the substrate 11 is low, the average light transmittance of the entire transparent conductor is lowered. Further, the average absorptance of light having a wavelength of 450 to 800 nm of the substrate 11 is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less.

The average transmittance of the base material 11 is a value measured by allowing measurement light to enter from an angle inclined by 5 ° with respect to the front surface of the base material 11. On the other hand, the average absorptance is a value calculated as [average absorptance = 100− (average transmittance + average reflectance)] by measuring the average reflectance of the substrate 11 in the same manner as the average transmittance. . Average transmittance and average reflectance are measured with a spectrophotometer.

The refractive index of the substrate 11 is preferably 1.40 to 1.95, more preferably 1.45 to 1.75, and still more preferably 1.45 to 1.70. The refractive index of the substrate 11 is usually determined by the material of the substrate 11. The refractive index of the substrate 11 is the refractive index of light having a wavelength of 510 nm, and is measured with an ellipsometer.

The thickness of the substrate 11 is preferably 1 μm to 20 mm, more preferably 10 μm to 2 mm. When the thickness of the base material 11 is thinner than 1 μm, the strength of the base material 11 becomes low, and there is a possibility that the base material 11 is damaged when an element is formed on the base material 11. Moreover, when the thickness of the base material 11 is too thick, it may cause the flexibility and light transmittance of the transparent conductor to decrease.

Examples of the glass include silica glass, soda lime silica glass, lead glass, borosilicate glass, and alkali-free glass. On the surface of these glass materials, from the viewpoints of adhesion to the laminated structure of the transparent conductor 10, durability, and smoothness, physical treatment such as polishing, coating films made of inorganic or organic materials, and the like, as necessary A hybrid film is formed by combining these films.

Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylates, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Is mentioned.

On the surface of the resin film, a film made of an inorganic material or an organic material or a hybrid film combining these films may be formed. Such coatings and hybrid coatings have a water vapor transmission rate (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) measured by a method according to JIS-K-7129-1992 of 0.01 g / ( m ² · 24 hours) or less of a barrier film (also referred to as a barrier film or the like) is preferable. Furthermore, the oxygen permeability measured by the method according to JIS-K-7126-1987 is 10 ⁻³ ml / (m ² · 24 hours · atm) or less, and the water vapor permeability is 10 ⁻⁵ g / (m ⁽² · 24 hours) or less is preferable.

As the material for forming the barrier film as described above, a material having a function of suppressing the intrusion of elements such as moisture and oxygen causing deterioration of the resin film is used. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Furthermore, in order to improve the brittleness of the barrier film, it is more preferable to have a laminated structure of these inorganic layers and layers (organic layers) made of an organic material. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma polymerization method, the atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used. In particular, the atmospheric pressure plasma polymerization method described in JP-A-2004-68143 can be preferably used.

[Organic compound layer]
The organic compound layer 12 is a layer provided on one main surface side of the substrate 11 and is provided adjacent to the conductive layer 15. The thickness of the organic compound layer 12 is 1 μm or less, preferably 100 nm or less.

The organic compound layer 12 is composed of a compound having a Lewis base. That is, the organic compound layer 12 is configured using a compound including an atom having an unshared electron pair. Examples of the compound having a Lewis base include nitrogen-containing compounds and sulfur-containing compounds.

For example, the organic compound layer 12 is a layer configured using at least one or both of a nitrogen-containing compound and a sulfur-containing compound. Moreover, it can also be set as the layer containing a multiple types of compound, respectively. The compound constituting the organic compound layer 12 may be a compound containing both nitrogen and sulfur.

The nitrogen-containing compound constituting the organic compound layer 12 may be a compound containing a nitrogen atom (N), and it is particularly preferable that the nitrogen atom has an unshared electron pair. Moreover, the sulfur containing compound which comprises the organic compound layer 12 should just be a compound containing the sulfur atom (S), and it is preferable that especially a sulfur atom has an unshared electron pair.

Further, the nitrogen-containing compound and the sulfur-containing compound constituting the organic compound layer 12 include a nitrogen atom or a sulfur atom having an unshared electron pair that is stably bonded to the metal material that is the main material constituting the conductive layer 15. Sometimes, this unshared electron pair of nitrogen atom or sulfur atom is referred to as [effective unshared electron pair]. The nitrogen-containing compound and the sulfur-containing compound constituting the organic compound layer 12 preferably have a content ratio of [effective unshared electron pairs] within a predetermined range.

Here, the “effective unshared electron pair” refers to an unshared electron pair that is not involved in aromaticity and is not coordinated to a metal among the unshared electron pairs of the nitrogen atom or sulfur atom contained in the compound. Suppose that The aromaticity here refers to an unsaturated cyclic structure in which atoms having π electrons are arranged in a ring, and is aromatic according to the so-called “Hückel's rule”. The condition is that the number is “4n + 2” (n = 0 or a natural number).

[Effective unshared electron pair] is a nitrogen atom or sulfur atom regardless of whether or not the nitrogen atom or sulfur atom itself provided with the unshared electron pair is a hetero atom constituting an aromatic ring. It is selected depending on whether or not the unshared electron pair possessed by is involved in aromaticity. For example, even if a nitrogen atom is a hetero atom constituting an aromatic ring, the lone pair of the nitrogen atom does not directly participate as an essential element in aromaticity, that is, a conjugated unsaturated ring If a non-shared electron pair is not involved in the delocalized π-electron system on the structure (aromatic ring) as an essential element for the expression of aromaticity, the unshared electron pair is [effective non-shared It is counted as one of the electron pairs. In contrast, even if a nitrogen atom is not a heteroatom that constitutes an aromatic ring, if all of the non-shared electron pairs of the nitrogen atom are involved in aromaticity, the nitrogen atom is not shared. An electron pair is not counted as a [valid unshared electron pair]. The same applies to sulfur atoms. In each compound, the number n of [effective unshared electron pairs] described above matches the number of nitrogen atoms and sulfur atoms having [effective unshared electron pairs].

Next, the [effective unshared electron pair] described above will be described in detail with a specific example.
The nitrogen atom is a Group 15 element and has 5 electrons in the outermost shell. Of these, three unpaired electrons are used for covalent bonds with other atoms, and the remaining two become a pair of unshared electron pairs. For this reason, the number of bonds of nitrogen atoms is usually three.

For example, as a group having a nitrogen atom, an amino group (—NR ¹ R ² ), an amide group (—C (═O) NR ¹ R ² ), a nitro group (—NO ₂ ), a cyano group (—CN), diazo Group (—N ₂ ), azide group (—N ₃ ), urea bond (—NR ¹ C═ONR ² —), isothiocyanate group (—N═C═S), thioamide group (—C (═S) NR ¹ R ² ) and the like. R ¹ and R ² are each a hydrogen atom (H) or a substituent.

The non-shared electron pair of the nitrogen atom constituting these groups does not participate in aromaticity and is not coordinated to the metal, and thus corresponds to [effective unshared electron pair]. Of these, the unshared electron pair possessed by the nitrogen atom of the nitro group (—NO ₂ ) is used for the resonance structure with the oxygen atom, but does not participate in aromaticity and is not coordinated to the metal [ It is thought that it exists on nitrogen as an effective unshared electron pair].

A nitrogen atom can also create a fourth bond by using an unshared electron pair. An example of this case will be described with reference to FIG. FIG. 2 shows a structural formula of tetrabutylammonium chloride (TBAC) and a structural formula of tris (2-phenylpyridine) iridium (III) [Ir (ppy) ₃ ].

Among these, TBAC is a quaternary ammonium salt in which one of four butyl groups is ionically bonded to a nitrogen atom and has a chloride ion as a counter ion. In this case, one of the electrons constituting the unshared electron pair of the nitrogen atom is donated to the ionic bond with the butyl group. For this reason, the nitrogen atom of TBAC is equivalent to the absence of an unshared electron pair in the first place. Therefore, the unshared electron pair of the nitrogen atom constituting TBAC does not correspond to the [effective unshared electron pair] that is not involved in aromaticity and coordinated to the metal.

Ir (ppy) ₃ is a neutral metal complex in which an iridium atom and a nitrogen atom are coordinated. The unshared electron pair of the nitrogen atom constituting this Ir (ppy) ₃ is coordinated to the iridium atom, and is utilized for coordination bonding. Therefore, the unshared electron pair of the nitrogen atom constituting Ir (ppy) ₃ does not correspond to the [effective unshared electron pair] that is not involved in aromaticity and coordinated to the metal.

Also, nitrogen atoms are common as heteroatoms that can constitute an aromatic ring, and can contribute to the expression of aromaticity. Examples of the “nitrogen-containing aromatic ring” include pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring and the like.

FIG. 3 is a diagram showing a structural formula and molecular orbitals of a pyridine ring which is one of the groups exemplified above. As shown in FIG. 3, in the conjugated (resonant) unsaturated ring structure in which the pyridine ring is arranged in a 6-membered ring, the number of delocalized π electrons is 6, so that 4n + 2 (n = 0 or natural number) Satisfy Hückel's law. Since the nitrogen atom in the 6-membered ring is substituted with —CH═, only one unpaired electron is mobilized to the 6π electron system, and the unshared electron pair is essential for the expression of aromaticity. Not involved as a thing.
Therefore, the unshared electron pair of the nitrogen atom constituting the pyridine ring corresponds to an [effective unshared electron pair] that does not participate in aromaticity and is not coordinated to the metal.

FIG. 4 shows the structural formula and molecular orbitals of the pyrrole ring. As shown in FIG. 4, the pyrrole ring has a structure in which one of the carbon atoms constituting the five-membered ring is substituted with a nitrogen atom, but the number of π electrons is also six and satisfies the Hückel rule. Nitrogen-containing aromatic ring. Since the nitrogen atom of the pyrrole ring is also bonded to a hydrogen atom, the lone pair is mobilized to the 6π electron system.

Therefore, although the nitrogen atom of the pyrrole ring has an unshared electron pair, this unshared electron pair is used as an essential element for the expression of aromaticity, and therefore does not participate in aromaticity and is a metal. It does not correspond to [Effective unshared electron pair] that is not coordinated to.

FIG. 5 is a diagram showing the structural formula and molecular orbitals of the imidazole ring. As shown in FIG. 5, the imidazole ring has a structure in which two nitrogen atoms N ¹ and N ² are substituted at the 1,3-positions in a 5-membered ring, and also has a nitrogen content of 6 π electrons. It is an aromatic ring. Of these, one nitrogen atom N ¹ is a pyridine ring-type nitrogen atom that mobilizes only one unpaired electron to the 6π-electron system and does not utilize the unshared electron pair for the expression of aromaticity, This unshared electron pair of nitrogen atom N ¹ corresponds to [effective unshared electron pair]. On the other hand, since the other nitrogen atom N ² is a pyrrole-ring-type nitrogen atom that mobilizes the unshared electron pair to the 6π electron system, the unshared electron pair of the nitrogen atom N ² is [effective Does not fall under “Unshared electron pair”.
Accordingly, in the imidazole ring, only the unshared electron pair of one nitrogen atom N ¹ out of the two nitrogen atoms N ¹ and N ² constituting the ring corresponds to the “effective unshared electron pair”.

The selection of the unshared electron pair at the nitrogen atom of the “nitrogen-containing aromatic ring” as described above is similarly applied to a condensed ring compound having a nitrogen-containing aromatic ring skeleton.

FIG. 6 shows the structural formula and molecular orbital of the δ-carboline ring. As shown in FIG. 6, the δ-carboline ring is a condensed ring compound having a nitrogen-containing aromatic ring skeleton, and is an azacarbazole compound in which a benzene ring skeleton, a pyrrole ring skeleton, and a pyridine ring skeleton are condensed in this order. Of these, the nitrogen atom N ³ of the pyridine ring mobilizes only one unpaired electron to the π-electron system, and the nitrogen atom N ⁴ of the pyrrole ring mobilizes an unshared electron pair to the π-electron system. Together with the 11 π electrons from the carbon atoms that are formed, the total number of π electrons is an aromatic ring of 14.

Therefore, among the two nitrogen atoms N ³ and N ⁴ of the δ-carboline ring, the unshared electron pair of the nitrogen atom N ³ constituting the pyridine ring corresponds to [effective unshared electron pair], but constitutes the pyrrole ring. The unshared electron pair of the nitrogen atom N ⁴ that does not correspond to [Effective unshared electron pair].

Thus, the unshared electron pair of the nitrogen atom constituting the condensed ring compound is involved in the bond in the condensed ring compound, similarly to the bond in the single ring such as the pyridine ring and pyrrole ring constituting the condensed ring compound. .

[Effective unshared electron pair] described above is important in order to express a strong interaction with silver which is the main component of the palladium-containing layer 13 and the metal layer 14 constituting the conductive layer 15. The nitrogen atom having such an [effective unshared electron pair] is preferably a nitrogen atom in the nitrogen-containing aromatic ring from the viewpoint of stability and durability. Therefore, the nitrogen-containing compound preferably has an aromatic heterocycle having a nitrogen atom having [effective unshared electron pair] as a heteroatom.

Particularly in the present embodiment, the number n of [effective unshared electron pairs] with respect to the molecular weight M of such a compound is defined as the effective unshared electron pair content [n / M]. The organic compound layer 12 is preferably composed of a compound selected such that [n / M] is 2.0 × 10 ⁻³ ≦ [n / M]. In addition, the nitrogen-containing compound and the sulfur-containing compound have an effective unshared electron pair content [n / M] defined as described above in a range of 3.9 × 10 ⁻³ ≦ [n / M]. Preferably, 6.5 × 10 ⁻³ ≦ [n / M] is more preferable.

Moreover, the organic compound layer 12 should just be comprised using the nitrogen containing compound and sulfur containing compound whose effective unshared electron pair content rate [n / M] is the predetermined range mentioned above, and only such a compound is used. You may be comprised, and you may be comprised using mixing such a compound and another compound. The other compound may or may not contain a nitrogen atom and a sulfur atom, and the effective unshared electron pair content [n / M] may not be within the predetermined range described above.

When the organic compound layer 12 is configured using a plurality of compounds, for example, based on the mixing ratio of the compounds, the molecular weight M of the mixed compound obtained by mixing these compounds is obtained, and [effective non- The total number n of [shared electron pairs] is obtained as an average value of the effective unshared electron pair content [n / M], and this value is preferably within the predetermined range described above. That is, it is preferable that the effective unshared electron pair content [n / M] of the organic compound layer 12 itself is in a predetermined range.

In addition, if the organic compound layer 12 is composed of a plurality of compounds and the composition ratio (content ratio) of the compounds is different in the thickness direction, the organic layer on the side in contact with the conductive layer 15 is used. The effective unshared electron pair content [n / M] in the surface layer of the compound layer 12 should just be a predetermined range.

Further, even when the organic compound layer 12 is made of a conductive material, it does not become a main electrode. For this reason, the organic compound layer 12 does not need to have a film thickness necessary as an electrode, and depending on the arrangement state of the transparent conductor 10 in an electronic device in which the transparent conductor 10 including the organic compound layer 12 is used, What is necessary is just to have the film thickness set appropriately.

Next, the details of the compounds constituting the organic compound layer 12 are described in terms of the method for forming the nitrogen-containing compound (1), the nitrogen-containing compound (2), the nitrogen-containing compound (3), the sulfur-containing compound, and the organic compound layer 12. These will be described in order.

[Nitrogen-containing compound (1)]
The nitrogen-containing compound constituting the organic compound layer 12 may be a compound containing a nitrogen atom (N). In particular, it is an organic compound containing a nitrogen atom having an unshared electron pair, and is preferably a compound described later.

(Compound I)
Hereinafter, specific examples (No. 1 to No. 48) of compounds satisfying the above-mentioned effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ ≦ [n / M] as nitrogen-containing compounds. ). Each compound No. 1-No. 48 is marked with a circle with respect to a nitrogen atom having [effective unshared electron pair]. Table 1 below shows these compound Nos. 1-No. The molecular weight M of 48, the number n of [effective unshared electron pairs], and the effective unshared electron pair content [n / M] are shown. In the copper phthalocyanine of the following compound 33, unshared electron pairs that are not coordinated to copper among the unshared electron pairs of the nitrogen atom are counted as [effective unshared electron pairs].

Table 1 shows the corresponding general formulas when these exemplary compounds also belong to the general formulas (1) to (8a) representing other compounds II described below.

[Nitrogen-containing compound (2)]
(Compound II)
Further, as the nitrogen-containing compound, other compounds may be used in addition to the compound whose effective unshared electron pair content [n / M] is within the predetermined range described above. As the nitrogen-containing compound, a compound containing a nitrogen atom is preferably used regardless of whether the effective unshared electron pair content [n / M] is in the predetermined range described above. Among them, a compound containing a nitrogen atom having [effective unshared electron pair] is particularly preferably used. Moreover, as a nitrogen-containing compound, the compound which has a property required for every electronic device to which the transparent conductor 10 provided with this nitrogen-containing compound is applied is used. For example, when the transparent conductor 10 is used as an electrode of an organic electroluminescent element, the nitrogen-containing compound is represented by the following general formulas (1) to (8a) from the viewpoint of formability. A compound having a structure is preferably used.

Among the compounds having the structures represented by the general formulas (1) to (8a), compounds that fall within the range of the effective unshared electron pair content [n / M] described above are included, and such compounds If so, it can be used alone as a nitrogen-containing compound (see Table 1 above). On the other hand, if the compound having the structure represented by the following general formulas (1) to (8a) is a compound that does not fall within the range of the effective unshared electron pair content [n / M], the effective unshared electron pair It is preferable to use it as a compound constituting the organic compound layer 12 by mixing with a compound having a content [n / M] in the above-mentioned range.

X11 in the above general formula (1) represents -N (R11)-or -O-. In the general formula (1), E101 to E108 each represent —C (R12) ═ or —N═. At least one of E101 to E108 is -N =. R11 and R12 each represent a hydrogen atom (H) or a substituent.

Examples of this substituent include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group). Etc.), cycloalkyl groups (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl groups (for example, vinyl group, allyl group, etc.), alkynyl groups (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon groups (aromatic Also referred to as aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group , Pyrenyl group, biphenylyl group), aromatic heterocyclic group (eg , Furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (above carbolinyl group) Any one of the carbon atoms constituting the carboline ring is substituted with a nitrogen atom), a phthalazinyl group, etc.), a heterocyclic group (eg, a pyrrolidyl group, an imidazolidyl group, a morpholyl group, an oxazolidyl group, etc.), an alkoxy group (For example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (For example, Enoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group) Etc.), arylthio groups (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl groups (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryl Oxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfo group) Nyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, Acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (For example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, Carbonyl group, etc.), amide groups (eg, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octyl) Carbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, Cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylamino Sulfonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido) Group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2 -Pyridylsulfinyl group etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino group, ethylamino group) Dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, piperidyl group (also referred to as piperidinyl group), 2,2,6, 6-tetramethylpiperidinyl group, etc.), halogen atoms (eg fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon groups (eg fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, penta Fluorophenyl group), cyano group Nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphate ester group (for example, dihexyl phosphoryl group, etc.), phosphorous acid An ester group (for example, diphenylphosphinyl group etc.), a phosphono group etc. are mentioned.

Some of these substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring. As these substituents, those not inhibiting the interaction between the compound and silver (Ag) are preferably used, and those having nitrogen having an effective unshared electron pair described above are particularly preferably applied. The above description regarding the substituents is similarly applied to the substituents shown in the description of the general formulas (2) to (8a) described below.

The compound having the structure represented by the general formula (1) as described above is preferable because it can exert a strong interaction between nitrogen in the compound and palladium or silver constituting the conductive layer 15.

The compound represented by the general formula (1a) is one form of the compound having the structure represented by the general formula (1), and is a compound in which X11 in the general formula (1) is —N (R11) —. . Such a compound is preferable because the above interaction can be expressed more strongly.

The compound represented by the general formula (1a-1) is one form of the compound having the structure represented by the general formula (1a), and is a compound in which E104 in the general formula (1a) is -N =. Such a compound is preferable because the above interaction can be expressed more effectively.

The compound represented by the general formula (1a-2) is another embodiment of the compound having the structure represented by the general formula (1a), and E103 and E106 in the general formula (1a) are set to -N =. A compound. Such a compound is preferable because the number of nitrogen atoms is large and the above interaction can be expressed more strongly.

The compound represented by the general formula (1b) is another embodiment of the compound having the structure represented by the general formula (1). In the general formula (1), X11 is —O—, and E104 is —N This is a compound marked with =. Such a compound is preferable because the above interaction can be expressed more effectively.

Furthermore, compounds represented by the following general formulas (2) to (8a) are preferable because the above interaction can be expressed more effectively.

The above general formula (2) is also a form of the general formula (1). In the general formula (2), Y21 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof. E201 to E216 and E221 to E238 each represent -C (R21) = or -N =. R21 represents a hydrogen atom (H) or a substituent. However, at least one of E221 to E229 and at least one of E230 to E238 represents -N =. k21 and k22 represent an integer of 0 to 4, and k21 + k22 is an integer of 2 or more.

In the general formula (2), examples of the arylene group represented by Y21 include o-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group, and biphenyldiyl. Groups (for example, [1,1′-biphenyl] -4,4′-diyl group, 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terphenyldiyl group, quaterphenyldiyl group And kinkphenyldiyl group, sexiphenyldiyl group, septiphenyldiyl group, octiphenyldiyl group, nobiphenyldiyl group, deciphenyldiyl group and the like.

In the general formula (2), examples of the heteroarylene group represented by Y21 include a carbazole ring, a carboline ring, a diazacarbazole ring (also referred to as a monoazacarboline ring, and one of carbon atoms constituting the carboline ring is nitrogen. The ring structure is replaced by an atom), a triazole ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a quinoxaline ring, a thiophene ring, an oxadiazole ring, a dibenzofuran ring, a dibenzothiophene ring, and an indole ring. And the like.

As a preferred embodiment of the divalent linking group consisting of an arylene group, heteroarylene group or a combination thereof represented by Y21, among the heteroarylene groups, a condensed aromatic heterocycle formed by condensation of three or more rings. A group derived from a condensed aromatic heterocyclic ring formed by condensing three or more rings is preferably included, and a group derived from a dibenzofuran ring or a dibenzothiophene ring is preferable. Are preferred.

In the general formula (2), it is preferable that 6 or more of E201 to E208 and 6 or more of E209 to E216 are each represented by -C (R21) =.

In the general formula (2), it is preferable that at least one of E225 to E229 and at least one of E234 to E238 represent -N =.

Furthermore, in the general formula (2), it is preferable that any one of E225 to E229 and any one of E234 to E238 represent -N =.

In the general formula (2), it is preferable that E221 to E224 and E230 to E233 are each represented by —C (R21) ═.

Further, in the compound having the structure represented by the general formula (2), it is preferable that E203 is represented by —C (R21) ═ and R21 represents a linking site, and E211 is also —C (R21). And R21 preferably represents a linking moiety.

Furthermore, E225 and E234 are preferably represented by -N =, and E221 to E224 and E230 to E233 are each preferably represented by -C (R21) =.

The general formula (3) is also a form of the general formula (1a-2). In the general formula (3), E301 to E312 each represent —C (R31) ═, and R31 represents a hydrogen atom (H) or a substituent. Y31 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof.

Moreover, in General formula (3), as a preferable aspect of the bivalent coupling group which consists of an arylene group represented by Y31, heteroarylene group, or those combinations, the thing similar to Y21 of General formula (2) is mentioned. .

The general formula (4) is also a form of the general formula (1a-1). In the general formula (4), E401 to E414 each represent —C (R41) ═, and R41 represents a hydrogen atom (H) or a substituent. Ar41 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring. Furthermore, k41 represents an integer of 3 or more.

In the general formula (4), when Ar41 represents an aromatic hydrocarbon ring, the aromatic hydrocarbon ring includes benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene Ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen And a ring, a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring. These rings may further have the substituents exemplified as R11 and R12 in the general formula (1).

In the general formula (4), when Ar41 represents an aromatic heterocycle, the aromatic heterocycle includes a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, Triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring And azacarbazole ring. The azacarbazole ring refers to one in which at least one carbon atom of the benzene ring constituting the carbazole ring is replaced with a nitrogen atom. These rings may further have the substituents exemplified as R11 and R12 in the general formula (1).

In the general formula (5), R51 represents a substituent. E501, E502, E511 to E515, and E521 to E525 each represent -C (R52) = or -N =. E503 to E505 each represent -C (R52) =. R52 represents a hydrogen atom (H) or a substituent. At least one of E501 and E502 is -N =, at least one of E511 to E515 is -N =, and at least one of E521 to E525 is -N =.

In the general formula (6), E601 to E612 each represent —C (R61) ═ or —N═, and R61 represents a hydrogen atom (H) or a substituent. Ar61 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring.

In the general formula (6), the substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring represented by Ar61 may be the same as Ar41 in the general formula (4).

In the general formula (7), R71 to R73 each represents a hydrogen atom (H) or a substituent, and Ar71 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

In the general formula (7), the aromatic hydrocarbon ring or aromatic heterocycle represented by Ar71 may be the same as Ar41 in the general formula (4).

The above general formula (8) is also a form of the general formula (7). In the general formula (8), R81 to R86 each represent a hydrogen atom (H) or a substituent. E801 to E803 each represent —C (R87) ═ or —N═, and R87 represents a hydrogen atom (H) or a substituent. Ar81 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

In the general formula (8), examples of the aromatic hydrocarbon ring or aromatic heterocycle represented by Ar81 include those similar to Ar41 in the general formula (4).

The nitrogen-containing compound having the structure represented by the general formula (8a) is one form of the nitrogen-containing compound having the structure represented by the general formula (8), and Ar81 in the general formula (8) is a carbazole derivative. . In the general formula (8a), E804 to E811 each represent —C (R88) ═ or —N═, and R88 represents a hydrogen atom (H) or a substituent. At least one of E808 to E811 is -N =, and E804 to E807 and E808 to E811 may be bonded to each other to form a new ring.

[Nitrogen-containing compound (3)]
(Compound III)
In addition to the compounds having the structures represented by the general formulas (1) to (8a) as described above, other compounds constituting the nitrogen-containing compound include compounds 1 to 166 shown below as specific examples. Is done. These compounds are compounds containing nitrogen atoms that interact with palladium and silver constituting the conductive layer 15. Further, these compounds are materials having an electron transport property or an electron injection property. Therefore, the transparent conductor 10 in which the organic compound layer 12 is formed using these compounds is suitable as a transparent electrode in the organic electroluminescent device, and the organic compound layer 12 as an electron transport layer or an electron injection layer in the organic electroluminescent device. Can be used. Among these compounds 1 to 166, compounds that fall within the range of the effective unshared electron pair content [n / M] described above are also included. It can be used as a constituent compound. Further, among these compounds 1 to 166, there are compounds that fall under the general formulas (1) to (8a) described above.

[Synthesis example of nitrogen-containing compound]
Specific examples of the synthesis of compound 5 are shown below as typical synthesis examples of the compound, but are not limited thereto.

Step 1: (Synthesis of Intermediate 1)
Under a nitrogen atmosphere, 2,8-dibromodibenzofuran (1.0 mol), carbazole (2.0 mol), copper powder (3.0 mol), potassium carbonate (1.5 mol), DMAc (dimethylacetamide) 300 ml Mixed in and stirred at 130 ° C. for 24 hours. The reaction solution thus obtained was cooled to room temperature, 1 L of toluene was added, washed with distilled water three times, the solvent was distilled off from the washed product under a reduced pressure atmosphere, and the residue was subjected to silica gel flash chromatography (n-heptane: Purification with toluene = 4: 1 to 3: 1) gave Intermediate 1 in a yield of 85%.

Step 2: (Synthesis of Intermediate 2)
Intermediate 1 (0.5 mol) was dissolved in 100 ml of DMF (dimethylformamide) at room temperature in the atmosphere, NBS (N-bromosuccinimide) (2.0 mol) was added, and the mixture was stirred overnight at room temperature. The resulting precipitate was filtered and washed with methanol, yielding intermediate 2 in 92% yield.

Step 3: (Synthesis of Compound 5)
Under a nitrogen atmosphere, intermediate 2 (0.25 mol), 2-phenylpyridine (1.0 mol), ruthenium complex [(η ₆ -C ₆ H ₆ ) RuCl ₂ ] ₂ (0.05 mol), triphenyl Phosphine (0.2 mol) and potassium carbonate (12 mol) were mixed in 3 L of NMP (N-methyl-2-pyrrolidone) and stirred at 140 ° C. overnight.

After cooling the reaction solution to room temperature, 5 L of dichloromethane was added, and the reaction solution was filtered. Subsequently, the solvent was distilled off from the filtrate under reduced pressure (800 Pa, 80 ° C.), and the residue was purified by silica gel flash chromatography (CH ₂ Cl ₂ : Et ₃ N = 20: 1 to 10: 1).

In a reduced-pressure atmosphere, the solvent was distilled off from the purified product, and the residue was dissolved again in dichloromethane and washed with water three times. The material obtained by washing was dried over anhydrous magnesium sulfate, and the solvent was distilled off from the dried material in a reduced-pressure atmosphere to obtain Compound 5 in a yield of 68%.

[Sulfur-containing compounds]
The sulfur-containing compound constituting the organic compound layer 12 may have a sulfide bond (also referred to as a thioether bond), a disulfide bond, a mercapto group, a sulfone group, a thiocarbonyl bond, etc. in the molecule. It preferably has a mercapto group.

Specifically, sulfur-containing compounds having structures represented by the following general formulas (9) to (12) can be given.

In the general formula (9), R ₇₁ and R ₇₂ each represent a substituent.

Examples of the substituent represented by R ₇₁ and R ₇₂ include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, An aryloxy group etc. are mentioned.

In the said General formula (10), _R73 and _R74 represent a substituent.
_Examples of the substituent represented by R ₇₃ and R ₇₄ include the same substituents as R ₇₁ and R ₇₂ .

In the above general formula (11), R ₇₅ represents a substituent.
_Examples of the substituent represented by R75 include the same substituents as _R71 and _R72 .

In the above general formula (12), R ₇₆ represents a substituent.
_Examples of the substituent represented by R76 include the same substituents as _R71 and _R72 .

Hereinafter, specific examples of the sulfur-containing compound applicable to the organic compound layer 12 are shown.

(Method for forming organic compound layer)
Examples of the method for forming the organic compound layer 12 include a method using a wet process such as a coating method, an inkjet method, a coating method, and a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, and a CVD method. And a method using a dry process such as Of these, the vapor deposition method is preferably applied.

Particularly, in the case where the organic compound layer 12 is formed using a plurality of compounds, co-evaporation in which a plurality of compounds are simultaneously supplied from a plurality of evaporation sources is applied. If a polymer material is used as the compound, a coating method is preferably applied. In this case, a coating solution in which the compound is dissolved in a solvent is used. The solvent in which the compound is dissolved is not limited. Furthermore, if the organic compound layer 12 is formed using a plurality of compounds, a coating solution may be prepared using a solvent capable of dissolving the plurality of compounds.

[Conductive layer]
The conductive layer 15 includes a metal layer 14 mainly composed of silver (Ag) that mainly constitutes the conductive layer 15, and a palladium-containing layer 13 containing palladium (Pd) provided adjacent to the metal layer 14. Is done.

The absorption of light by the conductive layer 15 is determined by the total of two absorptions, absorption inherent to metal (hereinafter, intrinsic absorption) and plasmon absorption mainly due to the surface shape of the conductive layer 15. The intrinsic absorption is smaller as the conductive layer 15 is thinner, and the plasmon absorption is smaller as the surface is smoother. Therefore, the conductive layer 15 is as thin as possible and the surface is smooth, which is effective in reducing light absorption by the conductive layer 15. It is.

The plasmon absorption rate of the conductive layer 15 is preferably 20% or less over the entire wavelength range of 400 nm to 800 nm. Furthermore, the plasmon absorption rate of the conductive layer 15 is preferably 15% or less, more preferably 7% or less, and further preferably 5% or less. When the plasmon absorptance at the wavelength is large, the light transmittance of the conductive layer 15 is lowered. Further, if there is a region having a large plasmon absorption rate in a part of the wavelength of 400 nm to 800 nm, the light transmitted through the conductive layer 15 is likely to be colored.

[Palladium-containing layer]
The palladium-containing layer 13 is a layer containing palladium (Pd) provided adjacent to the metal layer 14. In this example, the palladium-containing layer 13 is a layer formed directly on the organic compound layer 12.

Generally, when the metal layer 14 mainly composed of Ag is formed on a base material, Ag atoms attached to the base material generate a lump (nucleus) having a certain size while being surface diffused. Then, the initial thin film growth proceeds along the periphery of this lump (nucleus). For this reason, in the film | membrane of the formation initial stage, there exists a clearance gap between masses and it does not conduct | electrically_connect. When a lump further grows from this state and the thickness becomes about 15 μm, a part of the lump is connected and barely conducted. However, the film surface is not yet smooth and plasmon absorption is likely to occur.

On the other hand, when a growth nucleus of palladium (Pd) is formed on the organic compound layer 12 and the organic compound layer 12 in advance, a metal material such as Ag constituting the metal layer 14 is converted into the organic compound layer 12 or the palladium-containing layer 13. It becomes difficult to move on.
Moreover, Pd can make the space | interval of growth nuclei narrower than the space | interval of the lump formed by surface diffusion of Ag atoms. Therefore, when the Ag layer grows starting from the growth nucleus of Pd, a flat layer tends to be formed even if the thickness is small. That is, it is possible to form the metal layer 14 that is electrically conductive even if the thickness is small and that hardly causes plasmon absorption.

The above growth nuclei are formed of a metal that hardly diffuses on the organic compound layer 12. As such a metal, the above-described palladium (Pd) alone or a material containing palladium (Pd) as a main component can be used. For example, an alloy containing gold, platinum, cobalt, nickel, molybdenum, titanium, aluminum, chromium, nickel, or the like may be used for palladium (Pd).

The palladium-containing layer 13 is difficult to diffuse on the surface of the organic compound layer 12 and needs to have high affinity with a material mainly composed of Ag constituting the metal layer 14. Moreover, it is preferable that a dense and fine growth nucleus is obtained. For example, a desired layer (growth nucleus) can be obtained by forming a layer that grows using assist, such as ion-assisted deposition (IAD: Ion Assisted Deposition), while being crushed finely.

The average thickness of the palladium-containing layer 13 is preferably 3 nm or less, more preferably 0.1 nm or less, and still more preferably a monoatomic layer. The average thickness of the palladium-containing layer 13 is adjusted by the formation speed and the formation time.

Further, the palladium-containing layer 13 may be a continuous and homogeneous film, a film having a defect in which a metal atom containing Pd is not arranged or a discontinuous part in which a hole is formed, or a metal atom containing Pd is separated from each other. Thus, it may be a so-called island structure attached in a dispersed state. Preferably, the metal atoms containing Pd are attached to each other while being separated from each other.
Furthermore, it may be formed as a single layer composed of only the palladium-containing layer 13 or may be a layer mixed with a material mainly composed of Ag of the metal layer 14 formed on the palladium-containing layer 13.

The palladium-containing layer 13 can be formed by using a sputtering method or a vapor deposition method with a Pd growth nucleus having a thickness of 3 nm or less. Alternatively, a palladium-containing layer having a sufficient thickness can be formed, and this layer can be dry etched to leave a Pd growth nucleus having a thickness of 3 nm or less.

Examples of sputtering methods that can be used include ion beam sputtering, magnetron sputtering, reactive sputtering, bipolar sputtering, and bias sputtering. The sputtering time is appropriately selected according to the average thickness of the Pd growth nuclei to be formed and the formation speed. The sputter formation rate is preferably 0.1 to 15 Å / second, more preferably 0.1 to 7 Å / second.

On the other hand, as the vapor deposition method, for example, a vacuum vapor deposition method, an electron beam vapor deposition method, an ion plating method, an ion beam vapor deposition method, or the like can be used. The deposition time is appropriately selected according to the Pd layer (growth nucleus) to be formed and the formation speed. The deposition rate is preferably 0.1 to 15 Å / second, more preferably 0.1 to 7 Å / second.

Further, in the method of forming a palladium-containing layer having a sufficient thickness on the organic compound layer 12 and then dry etching the layer to a desired thickness, the method for forming the palladium-containing layer is not particularly limited. For example, a vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, or a thermal CVD method, or a wet deposition method such as a plating method can be used. The average thickness of the Pd-containing layer to be formed is preferably 3 to 15 nm, more preferably 5 to 10 nm. If the average thickness of the layer containing Pd is less than 3 nm, the amount of metal is small, and sufficient growth nuclei may not be obtained.

The dry etching method for the palladium-containing layer refers to an etching method that involves physical collision of etching gas, ions, radicals, etc., and does not include reactive gas etching that performs etching only by chemical reaction. The etching method is not particularly limited as long as it involves such physical collision, and for example, ion beam etching, reverse sputter etching, plasma etching, or the like can be used.
In particular, ion beam etching is particularly preferable from the viewpoint that desired unevenness is easily formed on the palladium-containing layer 13 (Pd growth nucleus) after etching.

If the palladium-containing layer 13 (Pd growth nucleus) is too thick, it is difficult to obtain a thin and smooth metal layer 14 even if the growth nucleus is formed. Furthermore, the metal layer 14 formed starting from the growth nucleus of the palladium-containing layer 13 becomes thicker. The average thickness of the growth nucleus of the palladium-containing layer 13 is determined from the difference between the thickness of the layer containing Pd and the etching thickness of the layer containing Pd. The etching thickness of the layer containing Pd is the product of the etching rate and the etching time. The etching rate is obtained from the time required for etching a layer containing Pd having a thickness of 50 nm separately formed on a glass substrate under the same conditions, and for the light transmittance after etching to be equal to that of the glass substrate (approximately 0 nm in thickness). The average thickness of the palladium-containing layer 13 (Pd growth nucleus) is adjusted by the dry etching time.

[Metal layer]
The metal layer 14 is a layer formed using silver or an alloy containing silver as a main component, which is formed adjacent to the palladium-containing layer 13.
The alloy mainly composed of silver (Ag) constituting the metal layer 14 is preferably an alloy containing 50% by mass or more of silver. As an example, an alloy mainly composed of silver (Ag) constituting the metal layer 14 includes silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), and silver indium (AgIn). ), Silver aluminum (AgAl), and the like.

The metal layer 14 as described above may have a structure in which silver or an alloy layer mainly composed of silver is divided into a plurality of layers as necessary.

Examples of the method for forming the metal layer 14 include a method using a wet process such as a coating method, an ink jet method, a coating method, a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, and the like. Examples include a method using a dry process. Of these, the vapor deposition method is preferably applied. In addition, the metal layer 14 is formed on the palladium-containing layer 13 so that it has sufficient conductivity even without a high-temperature annealing treatment after the formation. A high temperature annealing treatment or the like may be performed.

The metal layer 14 preferably has a thickness in the range of 3 to 15 nm. When the thickness is 15 nm or less, particularly 12 nm or less, the absorption component or reflection component of the layer can be suppressed low, and the light transmittance of the transparent conductor 10 is maintained, which is preferable. Moreover, if the metal layer 14 is at least 3 nm or more in thickness, the conductivity of the transparent conductor 10 is ensured.

Furthermore, in order not to inhibit the light transmittance of the transparent conductor 10, it is preferable to set the thickness of the metal layer 14 so that the total thickness of the metal layer 14 and the palladium-containing layer 13 is 15 nm or less. In particular, the total thickness is preferably 12 nm or less. A total thickness of the metal layer 14 and the palladium-containing layer 13 of 15 nm or less is preferable because the absorption component and reflection component of the layer can be kept low and the light transmittance of the transparent conductor 10 is maintained. Furthermore, the light transmittance of the transparent conductor 10 is further improved by setting the total thickness of the metal layer 14 and the palladium-containing layer 13 to 12 nm or less.

In addition, the conductive layer 15 including the palladium-containing layer 13 and the metal layer 14 provided adjacent to the palladium-containing layer 13 as described above may have an upper portion of the metal layer 14 covered with a protective film, Another conductive layer may be laminated. In this case, it is preferable that the protective film and the conductive layer have light transmittance so as not to impair the light transmittance of the transparent conductor 10.

[Effect of transparent conductor]
The transparent conductor 10 configured as described above includes a palladium-containing layer 13 and a metal layer 14 containing silver as a main component adjacent to an organic compound layer 12 configured using a compound containing a nitrogen atom. The conductive layer 15 is provided. According to this configuration, since the metal layer 14 mainly composed of silver is formed with the palladium-containing layer 13 as a growth nucleus, the diffusion distance of silver atoms on the formation surface is reduced by the interaction between Pd atoms and Ag atoms. It reduces and aggregation of silver is suppressed.
Further, by forming the palladium-containing layer 13 and the metal layer 14 adjacent to the organic compound layer 12, the interaction between Pd atoms and Ag atoms and the compound containing the nitrogen atoms constituting the organic compound layer 12. Thus, the diffusion distance of Pd atoms and Ag atoms on the surface of the organic compound layer 12 is reduced, and aggregation is suppressed.

In particular, the organic compound layer 12 is formed using a compound having an effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ ≦ [n / M] as an index of bond stability. By doing so, the effect of suppressing aggregation of the above-mentioned palladium and silver becomes remarkable.

That is, by using the organic compound layer 12 and the palladium-containing layer 13, a silver layer that is easily isolated in an island shape by growth in a nucleus growth type (Volumer-Weber: VW type) is generally formed as a single layer growth type. It is formed by the growth of (Frank-van der Merwe: FM type). For this reason, the conductive layer 15 having a uniform thickness is formed although the thickness is small.
Therefore, it is possible to configure the transparent conductor 10 that can suppress light absorption by the conductive layer 15 to ensure light transmission and further ensure conductivity.

<2. Transparent Conductor (Second Embodiment)>
Next, a second embodiment of the present invention will be described. In FIG. 7, the schematic block diagram (sectional drawing) of the transparent conductor of 2nd Embodiment is shown. As shown in FIG. 7, the transparent conductor 20 of the second embodiment is only provided with an admittance adjusting layer 21 between the base material 11 and the organic compound layer 12, and the transparent conductor 20 of the first embodiment shown in FIG. Different from the transparent conductor 10. Hereinafter, the detailed description which overlaps about the component similar to 1st Embodiment is abbreviate | omitted, and demonstrates the structure of the transparent conductor 20 of 2nd Embodiment.

[Configuration of transparent conductor]
As shown in FIG. 7, the transparent conductor 20 includes an admittance adjusting layer 21, an organic compound layer 12, and a conductive layer 15. The transparent conductor 20 is provided on the base material 11.
The conductive layer 15 includes a metal layer 14 mainly composed of silver and a palladium-containing layer 13 formed at a position adjacent to the metal layer 14. The palladium-containing layer 13 is configured to be sandwiched between the metal layer 14 and the organic compound layer 12.
In the organic compound layer 12, an admittance adjusting layer 21 is provided on the surface opposite to the surface on which the conductive layer 15 is formed.
The admittance adjusting layer 21 is provided between the organic compound layer 12 and the base material 11 and is directly formed on the base material 11.
That is, the transparent conductor 20 has a configuration in which the admittance adjusting layer 21, the organic compound layer 12, the conductive layer 15 including the palladium-containing layer 13 and the metal layer 14 are laminated on the base material 11 in this order.

In the transparent conductor 20 of the second embodiment, the organic compound layer 12, the conductive layer 15, and the palladium-containing layer 13 and the metal layer 14 constituting the conductive layer 15 have the same configuration as in the first embodiment. . In addition, the substrate 11 can have the same configuration as that of the first embodiment.
For this reason, detailed description is abbreviate | omitted about the structure of the base material 11, the organic compound layer 12, and the conductive layer 15, the palladium containing layer 13, and the metal layer 14 which are formed on this.

[Admittance adjustment layer]
The admittance adjustment layer 21 is a layer provided for adjusting optical characteristics such as reflectance and transmittance of the transparent conductor 20, in particular, the reflectance of the conductive layer 15. The admittance adjustment of the transparent conductor 20 by the admittance adjustment layer 21 will be described later.

The admittance adjusting layer 21 is preferably a layer containing a dielectric material or an oxide semiconductor material. The material constituting the admittance adjusting layer 21 is preferably a metal oxide or a metal sulfide. Examples of metal oxides or metal sulfides include titanium oxide (TiO ₂ : n = 2.1 to 2.4), indium tin oxide (ITO: n = 1.9 to 2.2), zinc oxide (ZnO : N = 1.9 to 2.0), zinc sulfide (ZnS: n = 2.0 to 2.2), niobium oxide (Nb ₂ O ₅ : n = 2.2 to 2.4), zirconium oxide ( ZrO ₂ : n = 2.0. To 2.1), cerium oxide (CeO ₂ : n = 1.9 to 2.2), tantalum pentoxide (Ta ₂ O ₅ : n = 1.9 to 2.2) ), Tin oxide (SnO ₂ : n = 1.8 to 2.0) and the like, and TiO ₂ and Nb ₂ O ₅ are preferable from the viewpoint of refractive index and productivity. The admittance adjusting layer 21 may include only one type of dielectric material or oxide semiconductor material, or may include two or more types.

The admittance adjusting layer 21 preferably has a higher refractive index than the layer in contact with the admittance adjusting layer 21 on the side opposite to the side where the organic compound layer 12 and the conductive layer 15 are provided. In this example, the admittance adjustment layer 21 preferably has a higher refractive index than the base material 11 on which the transparent conductor 20 is provided.

Further, the refractive index of the admittance adjusting layer 21 is preferably 1.8 or more, more preferably 2.1 or more and 2.5 or less. As will be described later, when the refractive index of the admittance adjusting layer 21 is higher than 1.8, the light transmittance of the transparent conductor 20 is likely to increase. Further, the refractive index of the admittance adjusting layer 21 is preferably greater than the refractive index of the substrate 11 by 0.1 to 1.1 or more, more preferably 0.4 to 1.0 or more. The refractive index of the admittance adjusting layer 21 is a refractive index of light having a wavelength of 510 nm, and is measured by an ellipsometer. The refractive index of the admittance adjustment layer 21 is adjusted by the material constituting the admittance adjustment layer 21, the density of the material in the admittance adjustment layer 21, and the like.

The thickness of the admittance adjusting layer 21 is preferably 10 to 150 nm, more preferably 20 to 80 nm. If the thickness of the admittance adjusting layer 21 is less than 10 nm, it is difficult to sufficiently enhance the light transmittance of the transparent conductor 20. On the other hand, when the thickness of the admittance adjusting layer 21 exceeds 150 nm, the transparency (antireflection property) of the transparent conductor 20 does not increase. The thickness of the admittance adjusting layer 21 is measured with an ellipsometer.

For forming the admittance adjusting layer 21, a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like can be used. From the viewpoint of increasing the refractive index (density) of the admittance adjusting layer 21, it is preferable to use an electron beam evaporation method or a sputtering method. In the case of the electron beam evaporation method, it is preferable to provide assistance such as IAD in order to increase the film density.

[Optical admittance of transparent conductor]
Next, the optical admittance of the transparent conductor 20 will be described. The admittance adjustment layer 21 of the transparent conductor 20 has a function of adjusting the intrinsic absorption and reflectance of the conductive layer 15.

Here, the reflectance R of the surface of the transparent conductor 20 is determined from the optical admittance y _{0 of the} medium on which light is incident and the equivalent admittance Y _{E of the} surface of the transparent conductor 20, and these relations are expressed by the following equations. Is done.

Based on the above formula, the reflectance R decreases as | y ₀ -Y _E | is closer to 0. Here, for example, if the medium on which light is incident is air, the optical admittance y _{0 of} air is 1. Therefore, the closer the equivalent admittance Y _E is to 1, the closer the reflectance R of the transparent conductor 20 is. Becomes lower.
As another example, when the organic EL layer is laminated on the transparent conductor 20, the optical admittance y ₀ of the medium the light is incident is a value determined by the refractive index of the material constituting the organic EL layer. For example, the organic EL layer, if having a structure in which a organic material having a refractive index of 1.8 on the transparent conductor 20, the optical admittance y ₀ of the medium the light is incident becomes 1.8. Therefore, as the equivalent admittance Y _E is the closer to 1.8, the reflectance of the transparent conductor 20 R is lowered.

The optical admittance Y is obtained from the ratio (H / E) between the electric field strength and the magnetic field strength, and is usually the same as the refractive index. The equivalent admittance Y _E is obtained from the optical admittance Y of each layer constituting the transparent conductor 20. For example, when the transparent conductor 20 is composed of one layer, the equivalent admittance Y _E of the transparent conductor 20 is equal to the optical admittance Y of the layer.

On the other hand, when the transparent conductor 20 is a laminate, the optical admittance Y _x (E _x H _x ) of the laminate from the first layer to the x layer is from the first layer to the (x−1) layer. It is represented by the product of the optical admittance Y _x-1 (E _x-1 H _x-1 ) of the laminate and a specific matrix, and specifically obtained by the following formula (1) or formula (2). .

・ When the x-th layer is a layer made of a dielectric material or an oxide semiconductor material

In the above formula, δ = 2πnd / λ, y = n (admittance of the x-th layer film), and d is the thickness of the x-th layer film.

・ When the xth layer is an ideal metal layer

In the above equation, γ = 2πkd / λ, d is the thickness of the x-th layer film, and k is the refractive index (imaginary part) of the film.

The optical admittance Yx (E _x H _x ) of the laminate from the transparent support material to the outermost layer when the x-th layer is the outermost layer becomes the equivalent admittance Y _E of the transparent conductor 20.

Here, FIG. 8 shows an admittance locus with a wavelength of 570 nm when the conductive layer 15 is formed directly on the substrate 11. FIG. 9 shows an admittance locus with a wavelength of 570 nm when the conductive layer 15 is formed on the substrate 11 via the admittance adjusting layer 21 and the organic compound layer 12.

In FIG. 8, the optical admittance at a wavelength of 570 nm at the interface of the conductive layer 15 on the substrate 11 side is Y ₁ = x ₁ + iy ₁ . On the other hand, in FIG. 9, the optical admittance having a wavelength of 570 nm on the admittance adjusting layer 21 side (organic compound layer 12 side) of the conductive layer 15 is Y ₁ = x ₁ + iy ₁ .
Further, in FIGS. 8 and 9, the optical admittance at the wavelength 570 nm of the interface on the opposite side of Y ₁ of the conductive layer 15 is Y ₂ = x ₂ + iy ₂ . This Y ₂ corresponds to the equivalent admittance Y _E of the transparent conductor 20. The interface opposite to Y ₁ is the interface opposite to the base material 11 of the conductive layer 15 in FIG. 8, and the admittance adjusting layer 21 side (organic compound layer 12 side) of the conductive layer 15 in FIG. It is the interface on the opposite side.

In the graph showing the admittance locus, the horizontal axis (Re) is the real part when the optical admittance Y is expressed as [Y = x + iy], that is, x in the equation. The vertical axis (IM) is the imaginary part of the optical admittance, that is, y in the equation.

The admittance locus shown in FIG. 8, the start point coordinates of admittance locus, an equivalent admittance Y _A conductive layer 15 side of the substrate 11, a admittance coordinates (x _{A, y} _A). Further, the equivalent admittance _{Y 2} of the interface of the base material 11 and the opposite side of the conductive layer 15 is admittance coordinates _(x 2, _{y 2).}

Since FIG. 8 shows the case where the conductive layer 15 is directly formed on the base material, the admittance coordinates (x ₁ , y ₁ ) of the equivalent admittance Y ₁ on the base material 11 side of the conductive layer 15 are the conductive layer 15. And the admittance coordinates (x _A , y _A ) of the equivalent admittance Y _A at the interface between the substrate 11 and the substrate 11.
Then, the starting-point of the admittance locus are the surface of the substrate 11, the refractive index of the substrate 11 side of the equivalent admittance _{Y 1} is a substrate 11 (e.g., n: 1.5) depending on the _{Y A} Y ₁ admittance coordinates (x _A , y _A ) = (x ₁ , y ₁ ) = (1.5, 0).

The admittance locus shown in FIG. 9, the coordinates of the start point of the admittance locus is the interface between the equivalent admittance _{Y A} of the substrate 11 and the admittance adjustment layer 21, the admittance coordinates _{_{(x A, y A) =}} (1.5, 0). The equivalent admittance Y _{B at} the interface between the admittance adjusting layer 21 and the organic compound layer 12 is represented by admittance coordinates (x _B , y _B ).
The equivalent admittance Y _{1 at} the interface between the conductive layer 15 and the organic compound layer 12 is expressed by admittance coordinates (x ₁ , y ₁ ). The equivalent admittance Y _{2 at} the interface of the conductive layer 15 opposite to the admittance adjustment layer 21 is the admittance coordinates (x ₂ , y ₂ ).

In the admittance locus shown in FIG. 9, the admittance locus is moved from the admittance coordinates (x _A , y _A ) to the admittance coordinates (x _B , y _B ) by providing the admittance adjustment layer 21. That is, the admittance locus is moved in the positive direction of the horizontal axis (real part) and the vertical axis (imaginary part) by the admittance adjustment layer 21.
Furthermore, by providing the organic compound layer 12, the admittance locus moves from the admittance coordinates (x _B , y _B ) to the admittance coordinates (x ₁ , y ₁ ) of the conductive layer 15. The admittance coordinates (x ₁ , y ₁ ) correspond to the optical admittance Y ₁ of the conductive layer 15 on the admittance adjustment layer 21 side (organic compound layer 12 side).

8 and 9, the coordinates of the end point of the admittance locus are the equivalent admittance Y _E of the transparent conductor 20. The distance between the admittance coordinates (x _E , y _E ) of the equivalent admittance Y _E of the transparent conductor 20 and the admittance coordinates (x ₀ , y ₀ ) of the optical admittance y ₀ of the medium on which light is incident is the transparent conductor 20 It is proportional to the reflectance R of the surface. That is, the closer the distance between the coordinates (x _E , y _E ) of the equivalent admittance Y _E and the admittance coordinates (x ₀ , y ₀ ) of the optical admittance y ₀ of the medium on which light enters, the closer the transparent conductor 20 is. The reflectance R becomes smaller.

As described above, the equivalent admittance Y _E of the transparent conductor 20 is equal to the equivalent admittance Y ₂ of the interface of the conductive layer 15 opposite to the admittance adjustment layer 21. Therefore, in this example, the distance between the admittance coordinates (x ₂ , y ₂ ) of the equivalent admittance Y ₂ of the conductive layer 15 and the admittance coordinates (x ₀ , y ₀ ) of the optical admittance y ₀ of the medium on which light is incident is The closer it is, the smaller the reflectance R of the transparent conductor 20 is.

For example, when the medium on which light is incident is air, the admittance coordinates (x ₀ , y ₀ ) = (1, ₀ ) of the optical admittance y ₀ are obtained from the refractive index (n: 1) of air. Further, if the organic layer such as an organic EL element, when the refractive index for example, n = 1.8 in the organic layer, admittance coordinates _(x _0, y 0) of the optical admittance _{y 0} = (1.8, 0).
Accordingly, the closer the admittance coordinates (x ₂ , y ₂ ) of the equivalent admittance Y ₂ of the conductive layer 15 are to the admittance coordinates (1, 0) and (1.8, 0) of the optical admittance y ₀ , the transparent conductor 20 The reflectance R becomes smaller.

Further, based on the relational expression between the reflectance R, the equivalent admittance Y _E , and the optical admittance y _{0 of the} medium on which light is incident, the coordinates (x _E , y _E ) of the equivalent admittance Y _E are incident on the light. If it is on the right side of the admittance coordinates (x ₀ , y ₀ ) of the medium to be reflected, the reflectance R tends to be small. Thus, x-coordinate _{x E} of the equivalent admittance _{Y E,} that is, x-coordinate _{x 2} of the equivalent admittance _{Y 2} of the conductive layer 15 is preferably larger than the x-coordinate _{x 0} of the optical admittance _{y 0} of the medium the light is incident .

In the transparent conductor 20 of this embodiment, the optical admittances at the wavelength of 570 nm of both main surfaces of the conductive layer 15 are Y ₁ and Y ₂ . Then, when optical admittance Y ₁ = x ₁ + iy ₁ and optical admittance Y ₂ = x ₂ + iy ₂ , at least one of x ₁ and x ₂ is 1.6 or more. Preferably, both x ₁ and x ₂ are 1.6 or more. That is, the horizontal axis coordinate (x coordinate) of at least one of Y ₁ (x ₁ , y ₁ ) and Y ₂ (x ₂ , y ₂ ) in the admittance locus in FIG. 9 is 1.6 or more. The reason is as follows.

In the case where the conductive layer 15 of the transparent conductor 20 is formed of a plurality of layers, the optical admittance at the interface of the conductive layer 15 of the layer closest to the admittance adjustment layer 21 (organic compound layer 12 side) is Y _1. = X ₁ + iy ₁ The optical admittance at the interface of the conductive layer 15 on the layer opposite to the admittance adjusting layer 21 (on the organic compound layer 12 side) is Y ₂ = x ₂ + iy ₂ .
Therefore, in the case of the conductive layer 15 including the metal layer 14 and the palladium-containing layer 13, the optical admittance at the interface of the palladium-containing layer 13 on the admittance adjusting layer 21 side is set to Y ₁ = x ₁ + iy ₁ . The optical admittance at the interface of the metal layer 14 on the side opposite to the admittance adjusting layer 21 side (organic compound layer 12 side) is Y ₂ = x ₂ + iy ₂ .

The metal material constituting the conductive layer 15 generally has a large value of the imaginary part of the optical admittance, and when the metal material is formed, the admittance locus greatly moves in the vertical axis (imaginary part) direction.
For example, when the conductive layer 15 is laminated directly on the base material 11 without providing the admittance adjustment layer 21, the base material 11 whose admittance locus is the start point (x _A , y _A ) as shown in FIG. 8 described above. From the admittance coordinates (1.5, 0) to (x ₂ , y ₂ ) in the vertical axis (imaginary part) direction. That is, the absolute value | y ₂ | of the imaginary part of the admittance coordinates becomes very large. Thus, when the absolute value of the imaginary part of the admittance coordinate increases, the optical admittance Y ₂ of the conductive layer 15 (equivalent admittance Y _E of the transparent conductor 20) becomes the admittance coordinate of the optical admittance y ₀ of the medium on which the light is incident. Move away from (x ₀ , y ₀ ). For this reason, the optical admittance Y ₂ of the conductive layer 15 is changed to the optical admittance y _{0 of the} medium on which light is incident, for example, the admittance coordinates (1, 0) of air or the admittance coordinates (1.8, 0) of organic material. It becomes difficult to get closer.

Further, the start point (x ₁ , y ₁ ) of the admittance locus, which is the admittance Y ₁ of the interface on the base material 11 side of the conductive layer 15, hardly moves from the admittance coordinates (1.5, 0) of the base material 11. It is difficult for the admittance trajectory to be symmetric about the horizontal axis of the graph. Thus, admittance locus and not about the horizontal axis line symmetry, in other wavelengths (other than 570 nm), admittance locus liable shake, the coordinates of the equivalent admittance Y _E is less likely to be constant. For this reason, a wavelength region in which the antireflection effect is not sufficient tends to occur.

On the other hand, in the admittance locus of wavelength 570 nm of the transparent conductor 20 provided with the base material 11 / the admittance adjusting layer 21 / the organic compound layer 12 / the conductive layer 15 in this order shown in FIG. The horizontal axis (real part) from the admittance coordinates (1.5, 0) of the base material 11 where the admittance coordinates (x ₁ , y ₁ ) of 15 admittances Y ₁ are the start points (x _A , y _A ) of the admittance locus And it moves largely in the positive direction of the vertical axis (imaginary part).
In particular, when the coordinates _{x 1} of the real part of _{Y 1} and 1.6 or more, the arc of the admittance locus increases, the admittance coordinates of admittance _{Y 1} of the conductive layer 15 _(x 1, _{y 1)} is the starting point of the admittance locus It greatly moves from (x _A , y _A ) in the positive direction of the imaginary part (vertical axis).

That is, even if the admittance locus is largely moved in the negative direction of the imaginary part by the conductive layer 15, the absolute value | y ₂ | of the imaginary part of Y ₂ is difficult to increase. Furthermore, the admittance locus of the conductive layer 15 tends to be line symmetric about the horizontal axis of the graph. Therefore, in other wavelengths (other than 570 nm), admittance locus tends linear symmetry around the horizontal axis of the graph, the coordinates of the equivalent admittance Y _E of each wavelength is approximately the same. That is, at any wavelength, the value of the equivalent admittance Y _E tends to approach the admittance coordinates (x ₀ , y ₀ ) of the optical admittance y ₀ of the medium on which light is incident. This indicates that a sufficient antireflection effect can be obtained at any wavelength.

When a metal material is used for the conductive layer 15, two sources can be considered for light absorption generated in the conductive layer 15. One is absorption inherent in the metal material, and the other is plasmon absorption resulting from the structure of the conductive layer 15. By keeping the admittance of the conductive layer 15 high, the inherent absorption of the metal material can be minimized.
Here, the following relational expression holds between the admittance Y at the interface of each layer and the electric field strength E existing in each layer.

Based on the above relational expression, as the admittance Y increases, the electric field strength E decreases and the electric field loss (absorption of light) is suppressed. Therefore, the admittance adjustment layer 21, adjusting the coordinates x ₁ of the real part of the admittance Y ₁ of the conductive layer 15 such that 1.6 or more, admittance Y ₁ of the conductive layer 15 is increased, the light by the conductive layer 15 Less absorption.

Further, the admittance adjustment layer 21, the real part coordinate x ₂ of the admittance Y ₂ of the conductive layer 15 when adjusted to 1.6 or more even, admittance Y ₂ of the conductive layer 15 is increased, the light by the conductive layer 15 Less absorption. Further, the admittance locus of the conductive layer 15 is likely to be line symmetric about the horizontal axis of the graph, and the electric field of the conductive layer 15 becomes small, so that light absorption by the conductive layer 15 is suppressed.

As described above, at least _one of x ₁ and x ₂ is preferably 1.6 or more and 7.0 or less. More preferably, _{x 1} and _{x 2} is both 1.6 to 7.0. More preferably, _{x 1} and / or _{x 2} is 1.8 to 5.5, further is preferably 1.9 to 3.0.

Also, among the _{x 1} and _{x 2,} it is preferably in particular _{x 1} is 1.6 or more. x ₁ is adjusted by the refractive index of the admittance adjusting layer 21, the thickness of the admittance adjusting layer 21, and the like. In this case, it is preferable that _{x 2} is 1.3 to 5.5, further preferably 1.5 to 3.5. x ₂ is the refractive index and the material of the conductive layer 15 is adjusted by the thickness and the like of the conductive layer 15.

Here, the absolute value | x ₁ −x ₂ | of the difference between x ₁ and x ₂ is preferably 1.5 or less, more preferably 1.0 or less, and even more preferably 0.8 or less. is there. Further, in particular, | x ₁ −x ₂ | / x _cross is preferably smaller than 0.5, more preferably, when the coordinate Ycross (x _cross , 0) of the intersection point between the admittance locus of the conductive layer 15 and the horizontal axis is used. Is 0.3 or less, more preferably 0.2 or less.

Moreover, since the center line of symmetry of the horizontal axis of the graph of admittance locus, a coordinate y ₁ of the imaginary part of the Y _1, the coordinate y ₂ of the imaginary part of Y _2, satisfy y ₁ × y _{2 <0} It is preferable.

Furthermore, the distance (| x _E −x ₀ |) between the coordinates (x _E , y _E ) of the equivalent admittance Y _E and the admittance coordinates (x ₀ , y ₀ ) of the optical admittance y ₀ of the medium on which light is incident. + | Y _E −y ₀ |) is preferably 0.9 or less, more preferably 0.6 or less, and still more preferably 0.3 or less.

[Effect of transparent conductor]
The transparent conductor 20 configured as described above has a configuration in which a conductive layer 15 in which a metal layer 14 is formed adjacent to the palladium-containing layer 13 is provided. Further, a conductive layer 15 composed of the palladium-containing layer 13 and the metal layer 14 is provided in contact with the organic compound layer 12. Thereby, when the metal layer 14 is formed adjacent to the palladium-containing layer 13, the palladium-containing layer of Ag atoms is formed by the interaction between the Ag atoms constituting the metal layer 14 and Pd constituting the palladium-containing layer 13. The diffusion distance on the surface 13 is reduced, and aggregation of the metal material is suppressed. At the same time, aggregation of palladium and the metal material is suppressed by the interaction between the organic compound layer 12 and Pd atoms and the interaction between the organic compound layer 12 and Ag atoms.
Therefore, in general, the metal layer 14 that is likely to be isolated in an island shape due to the growth of the nuclear growth type (Volumer-Weber: VW type) is caused by the growth of the single layer growth type (Frank-van der Merwe: FM type). Will be formed. Therefore, the thin conductive layer 15 having a uniform thickness can be obtained.

Further, the transparent conductor 20, the real part _{x 1} at the interface of the optical admittance _{Y 1} of the conductive layer 15, the real part _{x 2} optical admittance _{Y 2} is the admittance adjustment layer 21, adjusted to be 1.6 or more Has been. Thus, by adjusting the admittance at the interface of the conductive layer 15 with the admittance adjusting layer 21, reflection of the transparent conductor 20 can be suppressed, and light transmittance can be improved.

As a result of the above, it is possible to obtain the transparent conductor 20 in which conductivity is ensured while ensuring light transmittance. For this reason, in the transparent conductor 20, it becomes possible to aim at coexistence with the improvement of electroconductivity, and the improvement of light transmittance.

<3. Transparent Conductor (Third Embodiment)>
Next, a third embodiment of the present invention will be described. In FIG. 10, the schematic block diagram (sectional drawing) of the transparent conductor of 3rd Embodiment is shown. As shown in FIG. 10, the transparent conductor 30 of the third embodiment only includes a first admittance adjustment layer 31 and a second admittance adjustment layer 32 as the admittance adjustment layer 21. Different from the transparent conductor 10 of the embodiment. Hereinafter, the detailed description which overlaps about the component similar to 1st Embodiment is abbreviate | omitted, and demonstrates the structure of the transparent conductor 30 of 3rd Embodiment.

[Configuration of transparent conductor]
As shown in FIG. 10, the transparent conductor 30 includes a first admittance adjustment layer 31 and a second admittance adjustment layer 32 as the admittance adjustment layer 21, and further includes an organic compound layer 12 and a conductive layer 15. is there.
The organic compound layer 12 is sandwiched between the admittance adjusting layer 21 and the conductive layer 15 at a position adjacent to the palladium-containing layer 13 constituting the conductive layer 15. The conductive layer 15 includes a metal layer 14 and a palladium-containing layer 13 formed at a position adjacent to the metal layer 14. That is, in the conductive layer 15, the palladium-containing layer 13 is sandwiched between the metal layer 14 and the organic compound layer 12.

As described above, the transparent conductor 30 shown in FIG. 10 includes the second admittance adjusting layer 32, the first admittance adjusting layer 31, the organic compound layer 12, and the conductive layer 15. Formed on top.
That is, the transparent conductor 30 has a configuration in which the second admittance adjustment layer 32, the first admittance adjustment layer 31, the organic compound layer 12, the palladium-containing layer 13, and the metal layer 14 are laminated on the base material 11 in this order. It is.

In the transparent conductor 30 of the third embodiment, the organic compound layer 12 and the palladium-containing layer 13 and the metal layer 14 constituting the conductive layer 15 have the same configuration as in the first embodiment. The first admittance adjustment layer 31 can have the same configuration as the admittance adjustment layer of the transparent conductor according to the second embodiment described above. For this reason, detailed description is abbreviate | omitted about the structure of the 1st admittance adjustment layer 31, the organic compound layer 12 formed on this, the palladium containing layer 13 of the conductive layer 15, and the metal layer 14. FIG.

[Second admittance adjustment layer]
The second admittance adjustment layer 32 is a layer provided on the side where the conductive layer 15 is not formed, of the two layers constituting the admittance adjustment layer 21. That is, in the admittance adjustment layer 21, the first admittance adjustment layer 31 is provided on the side where the conductive layer 15 is formed, and the second admittance adjustment layer 32 is provided on the side opposite to the side where the conductive layer 15 is formed. ing.

The second admittance adjustment layer 32 is a layer having a lower refractive index than the first admittance adjustment layer 31. In particular, the second admittance adjustment layer 32 preferably has a refractive index lower than that of the first admittance adjustment layer 31 by 0.2 or more at a wavelength of 550 nm. The second admittance adjusting layer 32 is made of, for example, a material having a low refractive index and light transmittance. For example, magnesium fluoride (MgF ₂ : n = 1.37), lithium fluoride (LiF: n = 1.39), calcium fluoride (CaF ₂ : n = 1.43), aluminum fluoride (AlF ₃ : n = 1.38) or the like is used. For example, a low refractive index material generally used for an optical film is preferably used. Poly (1,1,1,3,3,3-hexafluoroisopropyl acrylate): n = 1.38, Poly (2,2,3,3,4,4,4-heptafluorobutyl acrylate): n = 1. 38, Poly (2,2,3,3,4,4,4-heptafluorobutyl methacrylate): n = 1.38, Poly (2,2,3,3,3-pentafluoropropyl acrylate): n = 1.39 Poly (1,1,1,3,3,3-hexafluoroisopropyl methacrylate): n = 1.39, Poly (2,2,3,4,4,4-hexafluorobutyl acrylate): n = 1.39, Poly ( 2,2,3,3,3-pentafluoropropyl methacrylate): n = 1.40, Poly (2,2,2-trifluoroethyl acrylate): n = 1.41, Poly (2,2,3,3-tetrafluoropropyl acrylate) ): Polymer material such as n = 1.42, Poly (2,2,3,3-tetrafluoropropyl methacrylate): n = 1.42, Poly (2,2,2-trifluoroethyl methacrylate): n = 1.42, etc. Is used.

The thickness of the second admittance adjusting layer 32 is preferably 40 to 200 nm, and more preferably 50 to 180 nm. If the thickness of the second admittance adjusting layer 32 is less than 40 nm or exceeds 200 nm, it is difficult to sufficiently increase the light transmittance of the transparent conductor 30. The thickness of the admittance adjusting layer 21 is measured with an ellipsometer.

[Optical admittance of transparent conductor]
Next, the optical admittance of the transparent conductor 30 will be described.
FIG. 11 shows an admittance locus of the transparent conductor 30 at a wavelength of 570 nm.

The optical admittance at a wavelength of 570 nm at the interface of the conductive layer 15 on the first admittance adjusting layer 31 side (organic compound layer 12 side) is Y ₁ = x ₁ + iy ₁ , and the conductive layer 15 is opposite to the first admittance adjusting layer 31. Let Y ₂ = x ₂ + iy ₂ be the optical admittance at a wavelength of 570 nm at the interface.
The admittance coordinates (x ₂ , y ₂ ) of the optical admittance Y ₂ of the conductive layer 15 correspond to the equivalent admittance Y _E of the transparent conductor 30.

The admittance locus shown in FIG. 11, the start point coordinates of admittance locus, an equivalent admittance Y _A conductive layer 15 side of the substrate 11, a admittance coordinates (x _{A, y} _A).
The transparent conductor 30 includes the second admittance adjustment layer 32 having a refractive index lower than that of the first admittance adjustment layer 31, so that the admittance locus is changed from the admittance coordinates (x _A , y _A ) to the admittance coordinates (x _B , Y _B ). The admittance coordinates (x _B , y _B ) move from the admittance coordinates (x _A , y _A ) in the negative direction of the vertical axis (imaginary part) and the horizontal axis (real part), and then the positive direction of the vertical axis (imaginary part) And the negative direction of the horizontal axis (real part), the positive direction of the vertical vertical axis (imaginary part) and the positive direction of the horizontal axis (real part), and the negative direction of the vertical axis (imaginary part) and the horizontal axis (real part) Move to draw a circle in the positive direction.
The admittance coordinates (x _B , y _B ) correspond to the optical admittance at the interface between the first admittance adjustment layer 31 and the second admittance adjustment layer 32.

Furthermore, as shown in FIG. 11, by providing the first admittance adjustment layer 31, the admittance locus moves from the admittance coordinates (x _B , y _B ) to the admittance coordinates (x _C , y _C ). That is, the first admittance adjustment layer 31 moves the admittance locus in the positive direction of the horizontal axis (real part) and the vertical axis (imaginary part).
Further, by providing the organic compound layer 12, the admittance locus moves from the admittance coordinates (x _C , y _C ) to the admittance coordinates (x ₁ , y ₁ ) of the conductive layer 15.

Thus, the first admittance adjusting layer 31, and, by providing the second admittance adjusting layer 32, so that the coordinates x ₁ of the real part of Y ₁ is 1.6 or more, the transparent conductor 30 admittance locus Can be adjusted. Further, the admittance locus of the conductive layer 15 can be brought close to line symmetry about the horizontal axis of the graph.
The action of the first admittance adjusting layer 31 on the transparent conductor 30 is the same as the action of the admittance adjusting layer on the transparent conductor described in the second embodiment.

As described above, the admittance locus can be adjusted to an arbitrary locus by including the second admittance adjustment layer 32 having a low refractive index. For this reason, compared with the case of the second embodiment described above that does not include the second admittance adjusting layer 32, the admittance coordinates (x ₁ , y ₁ ) of the optical admittance Y ₁ of the conductive layer 15 and the optical admittance Y ₂ Adjustment of the admittance coordinates (x ₂ , y ₂ ) can be easily performed.
As a result, the optical admittance Y ₂ of the conductive layer 15 is changed to the optical admittance y _{0 of the} medium on which light is incident, for example, the admittance coordinate (1, 0) of air, the admittance coordinate (1.8, 0) of organic material, etc. It is easy to approach the arbitrary coordinate position.

Therefore, the value of the equivalent admittance Y _E is, light is easily accessible to the admittance coordinates of the optical admittance y ₀ of the medium which enters (x _{0, y} _0), to reduce the reflectivity of the transparent conductor 30, the light permeability Can be improved. Further, the original absorption of the metal material can be minimized by keeping the admittance of the conductive layer 15 high.

As described above, when the admittance adjustment layer 21 is formed of a plurality of layers, the degree of freedom in design is improved by appropriately combining the materials and thicknesses constituting the admittance adjustment layer 21. For this reason, compared with the case where the admittance adjusting layer is formed as a single layer, the optical admittances Y ₁ and Y ₂ of the conductive layer 15 can be easily adjusted, and there is a range in which the optical admittances Y ₁ and Y ₂ can be optimized. spread.
Therefore, the light transmittance of the transparent conductor 30 can be improved by forming the admittance adjustment layer 21 from a plurality of layers like the first admittance adjustment layer 31 and the second admittance adjustment layer 32.

<4. Organic Electroluminescent Device (Fourth Embodiment)>
Next, a fourth embodiment of the present invention will be described. In the fourth embodiment, as an example of an electronic device, a bottom emission type organic electroluminescent element using the transparent conductor of the above-described third embodiment will be described. FIG. 12 is a cross-sectional configuration diagram of the organic electroluminescent element of this embodiment. The configuration of the organic electroluminescent element will be described below based on this figure.

[Configuration of organic electroluminescent element]
The organic electroluminescent element 40 shown in FIG. 12 is provided on the base material 11 which is a transparent substrate, and in order from the base material 11 side, the transparent conductor 30 serving as an anode, the light emitting functional layer 46, and a counter electrode serving as a cathode. An electrode 47 is laminated. Among these, the transparent conductor 30 of the above-described third embodiment is used as the transparent conductor 30. For this reason, the organic electroluminescent element 40 is configured as a bottom emission type in which generated light (hereinafter referred to as emitted light h) is extracted from at least the substrate 11 side.

Further, the overall layer structure of the organic electroluminescent element 40 is not limited to the above, and may be a general layer structure. Here, the transparent conductor 30 is disposed on the anode (ie, anode) side, and the metal layer 14 of the conductive layer 15 mainly functions as an anode, while the counter electrode 47 functions as a cathode (ie, cathode).

In this case, for example, the light emitting functional layer 46 includes [hole injection layer 46a / hole transport layer 46b / light emission layer 46c / electron transport layer 46d / electron injection layer 46e] in this order on the transparent conductor 30 serving as the anode. A stacked structure can be exemplified, and at least the light emitting layer 46c is formed using an organic material. The hole injection layer 46a and the hole transport layer 46b may be provided as a hole transport / injection layer having a hole transport property and a hole injection property. The electron transport layer 46d and the electron injection layer 46e may be provided as a single layer having electron transport properties and electron injection properties. Of these light emitting functional layers 46, for example, the electron injection layer 46e may be made of an inorganic material.

Further, in addition to these layers, the light-emitting functional layer 46 may be laminated with a hole blocking layer, an electron blocking layer, or the like as necessary. Further, the light emitting layer 46c has each color light emitting layer for generating light emission in each wavelength region, and each of these color light emitting layers is laminated through a non-light emitting intermediate layer to form a light emitting layer unit. Also good. The intermediate layer may function as a hole blocking layer and an electron blocking layer. Further, the counter electrode 47 as a cathode may also have a laminated structure as required. In such a configuration, only a portion where the light emitting functional layer 46 is sandwiched between the transparent conductor 30 and the counter electrode 47 becomes a light emitting region in the organic electroluminescent element 40.

Further, in the layer configuration as described above, an auxiliary electrode may be provided in contact with the conductive layer 15 of the transparent conductor 30 for the purpose of reducing the resistance of the transparent conductor 30.

Hereinafter, the details of the main layers for constituting the organic electroluminescent element 40 described above are as follows: the base material 11, the transparent conductor 30, the counter electrode 47, the light emitting layer 46 c of the light emitting functional layer 46, and other layers of the light emitting functional layer 46. And the auxiliary electrode will be described in this order. Then, the manufacturing method of the organic electroluminescent element 40 is demonstrated.

[Base material]
The base material 11 is made of a transparent material having optical transparency among the base materials on which the transparent conductor 30 of the first embodiment shown in FIG. 1 is provided.

[Transparent conductor (anode side)]
The transparent conductor 30 is the transparent conductor 30 of the above-described third embodiment. From the substrate 11 side, the second admittance adjustment layer 32, the first admittance adjustment layer 31, the organic compound layer 12, and the conductive layer 15 are used. Is a configuration formed in this order. Here, in particular, the conductive layer 15 constituting the transparent conductor 30 is a substantial anode.

[Counter electrode (cathode)]
The counter electrode 47 is a conductive layer that functions as a cathode for supplying electrons to the light emitting functional layer 46, and a metal, an alloy, an organic or inorganic conductive compound, and a mixture thereof are used. Specifically, gold, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO, TiO ₂ and oxide semiconductors such as SnO ₂ .

The counter electrode 47 can be produced by forming a thin layer of these conductive materials by a method such as vapor deposition or sputtering. The sheet resistance as the counter electrode 47 is several hundred Ω / sq. The following is preferable, and the thickness is usually selected in the range of 5 nm to 5 μm, preferably 5 nm to 200 nm.

[Light emitting layer]
The light emitting layer 46c used in the organic electroluminescent element of this embodiment contains, for example, a phosphorescent compound as a light emitting material.

The light emitting layer 46c is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer 46d and holes injected from the hole transport layer 46b, and the light emitting portion is the light emitting layer 46c. Even within the layer, it may be an interface with an adjacent layer in the light emitting layer 46c.

The structure of the light emitting layer 46c is not particularly limited as long as the light emitting material included satisfies the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting intermediate layer (not shown) between the light emitting layers 46c.

The total thickness of the light emitting layer 46c is preferably in the range of 1 to 100 nm, and more preferably 1 to 30 nm because it can be driven at a lower voltage. In addition, the sum total of the thickness of the light emitting layer 46c is a thickness also including the said intermediate | middle layer, when a nonluminous intermediate | middle layer exists between the light emitting layers 46c.

In the case of the light emitting layer 46c having a structure in which a plurality of layers are laminated, the thickness of each light emitting layer is preferably adjusted to a range of 1 to 50 nm, and more preferably adjusted to a range of 1 to 20 nm. When the plurality of stacked light emitting layers correspond to the respective emission colors of blue, green, and red, there is no particular limitation on the relationship between the thicknesses of the blue, green, and red light emitting layers.

The light emitting layer 46c as described above can be formed of a light emitting material or a host compound, which will be described later, by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method.

The light-emitting layer 46c may be a mixture of a plurality of light-emitting materials, or a phosphorescent light-emitting material and a fluorescent light-emitting material (also referred to as a fluorescent dopant or a fluorescent compound) may be mixed and used in the same light-emitting layer 46c.

The structure of the light emitting layer 46c preferably includes a host compound (also referred to as a light emitting host) and a light emitting material (also referred to as a light emitting dopant compound or a guest material) and emits light from the light emitting material.

(Host compound)
As the host compound contained in the light emitting layer 46c, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. Furthermore, the compound whose phosphorescence quantum yield is less than 0.01 is preferable. The host compound preferably has a volume ratio in the layer of 50% or more among the compounds contained in the light emitting layer 46c.

As the host compound, a known host compound may be used alone, or a plurality of types may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic electroluminescence device 40 can be made highly efficient. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

The host compound used may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .

As the known host compound, a compound having a high Tg (glass transition temperature) that has a hole transporting ability and an electron transporting ability and prevents the emission of light from being long-wavelength is preferable. The glass transition point (Tg) here is a value obtained by a method in accordance with JIS-K-7121 using DSC (Differential Scanning Colorimetry).

Specific examples of the host compound applicable to the organic electroluminescence device include compounds H1 to H79 described in paragraphs [0163] to [0178] of JP2013-4245A. The compounds H1 to H79 described in paragraphs [0163] to [0178] of JP2013-4245 are incorporated in the present specification.

Also, as specific examples of other known host compounds, compounds described in the following documents can be used. For example, Japanese Patent Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860 Gazette, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579 No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002-363227, No. 2002-231453. No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060. No. 2002-302516, No. 2002-305083, No. 2002-305084, No. 2002-308837, and the like.

(Luminescent material)
Examples of the light-emitting material that can be used in the organic electroluminescent element of this embodiment include phosphorescent compounds (also referred to as phosphorescent compounds and phosphorescent materials).

A phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, a phosphorescent compound emits phosphorescence at room temperature (25 ° C.), and a phosphorescence quantum yield of 0.01 at 25 ° C. Although defined as the above compounds, the preferred phosphorescence quantum yield is 0.1 or more.

The phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, when the phosphorescent compound is used in this example, the phosphorescence quantum yield (0.01 or more) is achieved in any solvent. It only has to be done.

There are two types of light emission principles of phosphorescent compounds. One is that recombination of carriers occurs on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent compound to obtain light emission from the phosphorescent compound. The other is a carrier trap type in which the phosphorescent compound becomes a carrier trap, and carriers are recombined on the phosphorescent compound to emit light from the phosphorescent compound. In either case, it is a condition that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

The phosphorescent compound can be appropriately selected from known materials used for the light emitting layer 46c of a general organic electroluminescent device, and preferably a group 8-10 metal in the periodic table of elements is used. It is a complex compound. More preferred are iridium compounds, osmium compounds, platinum compounds (platinum complex compounds), and rare earth complexes, and most preferred are iridium compounds.

In the organic electroluminescent element 40 of the present embodiment, at least one light emitting layer 46c may contain two or more types of phosphorescent compounds, and the concentration ratio of the phosphorescent compounds in the light emitting layer 46c is the light emitting layer 46c. It may change in the thickness direction.

The phosphorescent compound is preferably 0.1% by volume or more and less than 30% by volume with respect to the total amount of the light emitting layer 46c.

As the phosphorescent compound applicable to the organic electroluminescence device, the general formulas (4), (5), and (6) described in paragraphs [0185] to [0235] of JP2013-4245A can be used. Preferred examples include the compounds represented and exemplary compounds. As other exemplary compounds, Ir-46, Ir-47, and Ir-48 are shown below. Compounds represented by general formula (4), general formula (5) and general formula (6) described in paragraphs [0185] to [0235] of JP2013-4245A and exemplified compounds (Pt-1 to Pt) -3, Os-1, Ir-1 to Ir-45) are incorporated herein.

These phosphorescent compounds (also referred to as phosphorescent metal complexes) are preferably contained in the light emitting layer 46c as light emitting dopants, but are contained in organic functional layers other than the light emitting layer 46c. May be.

Further, the phosphorescent compound can be appropriately selected from known materials used for the light emitting layer 46c of the organic electroluminescent device 40.

The above phosphorescent compounds (also referred to as phosphorescent metal complexes) are, for example, OrganicOrLetters magazine vol.3 No.16 2579-2581 (2001), Inorganic Chemistry, Vol.30, No.8 1685-1687. (1991), J. Am. Chem. Soc., 123 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 704 1704-1711 (2001), Inorganic Chemistry, Vol. 41 No. 12 3055-3066 (2002), New Journal of 第 Chemistry., 26261171 (2002), European Journal of Organic Chemistry, Vol.4 695-709 (2004), further described in these documents Can be synthesized by applying a method such as the reference.

(Fluorescent material)
Fluorescent materials include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes Examples thereof include dyes, polythiophene dyes, and rare earth complex phosphors.

[Injection layer: hole injection layer, electron injection layer]
The injection layer is a layer provided between the electrode and the light emitting layer 46c in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and the forefront of its industrialization (November 30, 1998, NT. 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of “S. Co., Ltd.”), which includes a hole injection layer 46a and an electron injection layer 46e.

The injection layer can be provided as necessary. The hole injection layer 46a is disposed between the anode and the light emitting layer 46c or the hole transport layer 46b, and the electron injection layer 46e is disposed between the cathode and the light emitting layer 46c or the electron transport layer 46d.

The details of the hole injection layer 46a are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like. Specific examples thereof include phthalocyanine represented by copper phthalocyanine. Examples thereof include a layer, an oxide layer typified by vanadium oxide, an amorphous carbon layer, and a polymer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

The details of the electron injection layer 46e are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specifically represented by strontium, aluminum, and the like. Examples thereof include a metal layer, an alkali metal halide layer typified by potassium fluoride, an alkaline earth metal compound layer typified by magnesium fluoride, and an oxide layer typified by molybdenum oxide. The electron injection layer 46e is desirably a very thin layer, and its thickness is preferably in the range of 1 nm to 10 μm, although it depends on the material.

[Hole transport layer]
The hole transport layer 46b is made of a hole transport material having a function of transporting holes, and in a broad sense, the hole injection layer 46a and the electron blocking layer are also included in the hole transport layer 46b. The hole transport layer 46b can be provided as a single layer or a plurality of layers.

The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

As the hole transport material, those described above can be used, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' Di (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino -(2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two described in US Pat. No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-30 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 688 are linked in a starburst type ( MTDATA) and the like.

Further, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

Also, so-called p-type hole transport materials as described in JP-A-11-251067, J. Huang et al., Applied Physics Letters, 80 (2002), p. 139 can be used. . These materials are preferably used because a highly efficient light-emitting element can be obtained.

The hole transport layer 46b is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. be able to. The thickness of the hole transport layer 46b is not particularly limited, but is usually about 5 nm to 5 μm, preferably 5 to 200 nm. The hole transport layer 46b may have a single layer structure made of one or more of the above materials.

It is also possible to increase the p property by doping impurities into the material of the hole transport layer 46b. Examples thereof include those described in JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Appl. Phys., 95, 5773 (2004), and the like. .

Thus, it is preferable to increase the p property of the hole transport layer 46b because an element with lower power consumption can be manufactured.

[Electron transport layer]
The electron transport layer 46d is made of a material having a function of transporting electrons. In a broad sense, the electron injection layer 46e and a hole blocking layer (not shown) are also included in the electron transport layer 46d. The electron transport layer 46d can be provided as a single layer structure or a stacked structure of a plurality of layers.

As an electron transport material (also serving as a hole blocking material) constituting the layer portion adjacent to the light emitting layer 46c in the electron transport layer 46d having a single layer structure and the electron transport layer 46d having a multilayer structure, electrons injected from the cathode are used. What is necessary is just to have the function to transmit to the light emitting layer 46c. As such a material, any one of conventionally known compounds can be selected and used. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives. Further, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group are also used as the material for the electron transport layer 46d. Can do. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq3), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, A metal complex replaced with Cu, Ca, Sn, Ga, or Pb can also be used as a material for the electron transport layer 46d.

In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the material for the electron transport layer 46d. Further, a distyrylpyrazine derivative exemplified also as the material of the light emitting layer 46c can be used as the material of the electron transport layer 46d. Similarly to the hole injection layer 46a and the hole transport layer 46b, n-type Si, n An inorganic semiconductor such as type-SiC can also be used as the material of the electron transport layer 46d.

The electron transport layer 46d can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. The film thickness of the electron transport layer 46d is not particularly limited, but is usually about 5 nm to 5 μm, preferably 5 to 200 nm. The electron transport layer 46d may have a single layer structure composed of one or more of the above materials.

It is also possible to increase the n property by doping the electron transport layer 46d with impurities. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like. Furthermore, it is preferable that the electron transport layer 46d contains potassium or a potassium compound. As the potassium compound, for example, potassium fluoride can be used. Thus, when the n property of the electron transport layer 46d is increased, a device with lower power consumption can be manufactured.

Moreover, as a material (electron transporting compound) of the electron transport layer 46d, for example, the above-mentioned compound No. 1-No. It is preferable to use 48 nitrogen-containing compounds, nitrogen-containing compounds represented by the above general formulas (1) to (8a), and nitrogen-containing compounds 1 to 166 described above.
Further, the sulfur-containing compounds represented by the general formulas (9) to (12), the above-described 1-1 to 1-9, 2-1 to 2-11, 3-1 to 3-23, and 4 It is preferable to use a sulfur-containing compound of -1.

[Blocking layer: hole blocking layer, electron blocking layer]
As described above, the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film. For example, it is described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237. There is a hole blocking (hole blocking) layer.

The hole blocking layer has a function of the electron transport layer 46d in a broad sense. The hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved. Moreover, the structure of the electron carrying layer 46d mentioned later can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer 46c.

On the other hand, the electron blocking layer has the function of the hole transport layer 46b in a broad sense. The electron blocking layer is made of a material that has a function of transporting holes but has a very small ability to transport electrons, and improves the probability of recombination of electrons and holes by blocking electrons while transporting holes. be able to. Moreover, the structure of the positive hole transport layer 46b mentioned later can be used as an electron blocking layer as needed. The thickness of the blocking layer is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

[Auxiliary electrode]
The auxiliary electrode is provided for the purpose of reducing the resistance of the transparent conductor 30, and is provided in contact with the conductive layer 15 of the transparent conductor 30. The material for forming the auxiliary electrode is preferably a metal having low resistance such as gold, platinum, silver, copper, or aluminum. Since these metals have low light transmittance, a pattern is formed in a range not affected by extraction of the emitted light h from the light extraction surface. Examples of a method for forming such an auxiliary electrode include a vapor deposition method, a sputtering method, a printing method, an ink jet method, and an aerosol jet method. The line width of the auxiliary electrode is preferably 50 μm or less from the viewpoint of the aperture ratio for extracting light, and the thickness of the auxiliary electrode is preferably 1 μm or more from the viewpoint of conductivity.

[Encapsulant]
The sealing material covers the organic electroluminescent element 40, and a plate-like (film-like) sealing member may be fixed to the base material 11 side by an adhesive, or a sealing layer. Good. This sealing material is provided so as to cover at least the light emitting functional layer 46 in a state where the terminal portions of the transparent conductor 30 and the counter electrode 47 in the organic electroluminescent element 40 are exposed. Further, an electrode may be provided on the sealing material so that the transparent conductor 30 of the organic electroluminescent element 40 and the terminal portion of the counter electrode 47 are electrically connected to this electrode.

Specific examples of the plate-like (film-like) sealing material include a glass substrate and a polymer substrate, and these substrate materials may be used in the form of a thinner film. Examples of the glass substrate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

In particular, since the element can be thinned, a polymer substrate in the form of a thin film can be preferably used as a sealing material.

Further, the polymer substrate in the form of a film has an oxygen permeability measured by a method according to JIS-K-7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, and JIS-K. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to −7129-1992 is 1 × 10 ⁻³ g / (m ² · 24 h) or less It is preferable that

Further, the above substrate material may be processed into a concave plate shape and used as a sealing material. In this case, the above-described substrate member is subjected to processing such as sandblasting or chemical etching, and is formed into a concave shape.

Further, the present invention is not limited to this, and a metal material may be used. Examples of the metal material include one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum. By using such a metal material as a sealing material in the form of a thin film, the entire light-emitting panel provided with the organic electroluminescent element can be thinned.

Moreover, the adhesive for fixing such a plate-shaped sealing material to the base material 11 side is for sealing the organic electroluminescent element 40 sandwiched between the sealing material and the base material 11. Used as a sealant. Specific examples of such an adhesive include photocuring and thermosetting adhesives having a reactive vinyl group of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing types such as 2-cyanoacrylates. Mention may be made of adhesives.

Also, examples of such an adhesive include epoxy-based heat and chemical curing types (two-component mixing). Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

In addition, the organic material which comprises the organic electroluminescent element 40 may deteriorate with heat processing. For this reason, it is preferable to use an adhesive that can be adhesively cured from room temperature to 80 ° C. Further, a desiccant may be dispersed in the adhesive.

Application of the adhesive to the bonding portion between the sealing material and the base material 11 may be performed using a commercially available dispenser or may be printed like screen printing.

Further, when a gap is formed between the plate-shaped sealing material, the base material 11 and the adhesive, this gap has an inert gas such as nitrogen or argon or fluorinated carbonization in the gas phase and the liquid phase. It is preferable to inject an inert liquid such as hydrogen or silicon oil. A vacuum is also possible. Moreover, a hygroscopic compound can also be enclosed inside.

Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate, and the like), and anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.

On the other hand, when a sealing layer is used as the sealing material, the light emitting functional layer 46 in the organic electroluminescent element 40 is completely covered and the terminal portions of the transparent conductor 30 and the counter electrode 47 in the organic electroluminescent element 40 are exposed. Thus, a sealing layer is provided on the substrate 11.

Such a sealing layer is composed of an inorganic material or an organic material. In particular, it is made of a material having a function of suppressing entry of a substance that causes deterioration of the light emitting functional layer 46 in the organic electroluminescent element 40 such as moisture and oxygen. As such a material, for example, an inorganic material such as silicon oxide, silicon dioxide, or silicon nitride is used. Further, in order to improve the brittleness of the sealing layer, a layered structure may be formed by using a layer made of an organic material together with a layer made of these inorganic materials.

The method for forming these layers is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

[Protective layer, protective plate]
In addition, although illustration is abbreviate | omitted here, you may provide a protective layer or a protective board between the base materials 11 on both sides of an organic electroluminescent element and a sealing material. This protective layer or protective plate is for mechanically protecting the organic electroluminescent element, and particularly when the sealing material is a sealing layer, sufficient mechanical protection is provided for the organic electroluminescent element EL. Therefore, it is preferable to provide such a protective layer or protective plate.

As the above protective layer or protective plate, a glass plate, a polymer plate, a thinner polymer film, a metal plate, a thinner metal film, a polymer material film or a metal material film is applied. Among these, it is particularly preferable to use a polymer film because it is lightweight and thin.

[Method for Fabricating Organic Electroluminescent Device]
Here, as an example, a method for manufacturing the organic electroluminescent element 40 shown in FIG. 12 will be described.

First, the second admittance adjusting layer 32 is formed on the substrate 11 to a thickness of about 90 nm. Next, the first admittance adjustment layer 31 is formed to a thickness of about 40 nm.
Next, the organic compound layer 12 is formed to a thickness of about 3 nm on the first admittance adjustment layer 31.
The formation of the first admittance adjustment layer 31 and the second admittance adjustment layer 32 includes a vapor deposition method (EB method and the like), a sputtering method, and the like. From the viewpoint that a dense layer can be easily obtained, an ion-assisted EB vapor deposition method or a sputtering method is used. Is particularly preferred.
Next, a palladium-containing layer 13 is formed on the organic compound layer 12 to a thickness of about 1 nm, and then a metal layer 14 made of a metal material is formed to a thickness of 3 nm to 15 nm. The palladium-containing layer 13 and the metal layer 14 can be formed by the method described in the first embodiment.
In this way, the anode-side transparent conductor 30 is produced on the substrate 11.

Next, a hole injection layer 46a, a hole transport layer 46b, a light emitting layer 46c, an electron transport layer 46d, and an electron injection layer 46e are formed in this order, and the light emitting functional layer 46 is formed. The formation of each of these layers includes a spin coating method, a casting method, an ink jet method, a vapor deposition method, a sputtering method, a printing method, etc., but it is easy to obtain a homogeneous layer, and pinholes are difficult to generate. Vacuum deposition or spin coating is particularly preferred. Further, different formation methods may be applied for each layer. When a vapor deposition method is employed for forming each of these layers, the vapor deposition conditions vary depending on the type of compound used, but generally the boat heating temperature storing the compound is 50 ° C. to 450 ° C., and the degree of vacuum is 10 ⁻⁶ Pa to 10 ^−. It is desirable to select each condition as appropriate within a range of ² Pa, a deposition rate of 0.01 nm / second to 50 nm / second, a substrate temperature of −50 ° C. to 300 ° C., and a thickness of 0.1 μm to 5 μm.

Next, the counter electrode 47 to be the cathode is formed by an appropriate forming method such as vapor deposition or sputtering. At this time, a pattern is formed in a shape in which terminal portions are drawn out from the upper side of the light emitting functional layer 46 to the periphery of the base material 11 while maintaining the insulating state with respect to the transparent conductor 30 by the light emitting functional layer 46.

Thereby, the organic electroluminescent element 40 is obtained. Thereafter, a sealing material that covers at least the light emitting functional layer 46 is provided in a state where the terminal portions of the transparent conductor 30 and the counter electrode 47 in the organic electroluminescent element 40 are exposed. At this time, the sealing material is adhered to the base material 11 side using an adhesive, and the organic electroluminescent element 40 is sealed between the sealing material and the base material 11.

Thus, a desired organic electroluminescent element 40 is obtained on the substrate 11. In the production of such an organic electroluminescent element 40, it is preferable to produce the light emitting functional layer 46 to the counter electrode 47 consistently by a single evacuation. However, the substrate 11 is taken out from the vacuum atmosphere on the way and is different. A forming method may be applied. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

When a DC voltage is applied to the organic electroluminescence device 40 thus obtained, the conductive layer 15 serving as an anode has a positive polarity and the counter electrode 47 serving as a cathode has a negative polarity, so that the voltage is 2V or more and 40V. Luminescence can be observed when the following is applied. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

In the above-described embodiment, the configuration in which the transparent conductor according to the third embodiment is applied to the bottom emission type organic electroluminescence device is described. However, the transparent conductor according to the first embodiment or the second embodiment is described. An organic electroluminescent element can also be configured using
Furthermore, the organic electroluminescent element to which these transparent conductors are applied is not limited to the bottom emission type, for example, a top emission type configuration in which light is extracted from the counter electrode side, or a dual emission type configuration in which light is extracted from both sides. It is good. If the organic electroluminescent device is a top emission type, a transparent material is used for the counter electrode, and an opaque base material having reflectivity is used instead of the base material of the transparent conductor, and the emitted light h is reflected by the substrate. It is also possible to take out from the counter electrode side. If the organic electroluminescent element is a double-sided light emitting device, a transparent material may be used for the counter electrode in the same manner as the transparent conductor, and the emitted light h may be extracted from both sides.
Also, in the bottom emission type, top emission type, and double-sided emission type organic electroluminescent elements, the transparent electroconductive element is used in addition to the transparent electroconductive element as in the fourth embodiment. The present invention can also be applied to a configuration in which a conductor is a cathode.

[Applications of organic electroluminescent devices]
Since the organic electroluminescent element of each embodiment mentioned above is a surface light emitter as mentioned above, it can be used as various light emission sources. For example, lighting devices such as home lighting and interior lighting, backlights for clocks and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, Examples include, but are not limited to, a light source of an optical sensor, and can be effectively used as a backlight of a liquid crystal display device combined with a color filter and a light source for illumination.

In addition, the organic electroluminescence device of each embodiment may be used as a kind of lamp for illumination or exposure light source, or a projection device for projecting an image, or directly viewing a still image or a moving image. It may be used as a type of display device (display). In this case, the area of the light emitting surface may be increased by so-called tiling, in which the light emitting panels provided with the organic electroluminescent elements are planarly joined together with the recent increase in size of the lighting device and the display.

The drive method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. A color or full-color display device can be produced by using two or more organic electroluminescence elements of the present invention having different emission colors.

<5. Lighting Device (Fifth Embodiment)>
[Lighting device-1]
A fifth embodiment of the present invention will be described. 5th Embodiment demonstrates the illuminating device using the organic electroluminescent element of the above-mentioned 4th Embodiment as an example of an electronic device.

The organic electroluminescent element used in the illumination device of the present embodiment may be designed such that the organic electroluminescent element having the configuration of the fourth embodiment described above has a resonator structure. Examples of the purpose of use of the organic electroluminescence device configured as a resonator structure include, but are not limited to, a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processor, a light source of an optical sensor, and the like. Not. Moreover, you may use for the said use by making a laser oscillation.

The material used for the organic electroluminescent element can be applied to an organic electroluminescent element that emits substantially white light (also referred to as a white organic electroluminescent element). For example, a plurality of light emitting materials can simultaneously emit a plurality of light emission colors to obtain white light emission by color mixing. As a combination of a plurality of emission colors, three emission maximum wavelengths of three primary colors of red, green, and blue may be included, or two emission using a complementary color relationship such as blue and yellow, blue green and orange, etc. A maximum wavelength may be included.

In addition, a combination of light emitting materials for obtaining a plurality of emission colors includes a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescent or phosphorescent light, and light from the light emitting material as excitation light. A combination with a dye material that emits light may also be used. In the white organic electroluminescent device, a plurality of light emitting dopants may be combined and mixed.

Such a white organic electroluminescent element is different from a configuration in which organic electroluminescent elements emitting each color are individually arranged in parallel to obtain white light emission, and the organic electroluminescent element itself emits white light. For this reason, a mask is not required for the formation of most layers constituting the element, and for example, a conductive layer can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, etc., and productivity is improved. .

Moreover, there is no restriction | limiting in particular as a luminescent material used for the light emitting layer of such a white organic electroluminescent element, For example, if it is a backlight in a liquid crystal display element, it will match the wavelength range corresponding to CF (color filter) characteristic. As described above, the metal complex described in the embodiment of the organic electroluminescent device described above or any material selected from known light-emitting materials may be selected and combined to be whitened.

If the white organic electroluminescent element described above is used, it is possible to produce a lighting device that emits substantially white light.

[Lighting device-2]
Further, the lighting device can increase the area of the light emitting surface by using, for example, a plurality of organic electroluminescent elements. In this case, the light emitting surface is enlarged by arranging (that is, tiling) a plurality of light emitting panels provided with organic electroluminescent elements on a base material on a support substrate. The support substrate may also serve as a sealing material, and each light-emitting panel is tiled in a state where the organic electroluminescence element is sandwiched between the support substrate and the base material of the light-emitting panel. An adhesive may be filled between the support substrate and the base material, thereby sealing the organic electroluminescent element. Note that the terminals of the transparent conductor and the counter electrode are exposed around the light emitting panel.

In the lighting device having such a configuration, the center of each light emitting panel is a light emitting region, and a non-light emitting region is generated between the light emitting panels. For this reason, a light extraction member for increasing the amount of light extracted from the non-light-emitting area may be provided in the non-light-emitting area of the light extraction surface. As the light extraction member, a light collecting sheet or a light diffusion sheet can be used.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Production of transparent conductor]
Each of the transparent conductors of Samples 101 to 128 was manufactured so that the area of the conductive region was 5 cm × 5 cm. Table 2 below shows the configuration of each transparent conductor of Samples 101 to 128.

[Preparation of transparent conductors of samples 101 and 102]
In the following manner, a metal layer made of silver was formed on a polyethylene terephthalate (PET) base material with each thickness shown in Table 2 below.

First, a base material made of PET was fixed to a base material holder of a commercially available vacuum vapor deposition apparatus and attached to a vacuum tank of the vacuum vapor deposition apparatus. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the said vacuum chamber. Next, after depressurizing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the resistance heating boat was energized and heated, and each of the metal layers made of silver was deposited at a deposition rate of 0.1 nm / second to 0.2 nm / second. Formed in thickness. The sample 101 was formed with a thickness of 8 nm, and the sample 102 was formed with a thickness of 12 nm.

[Production of transparent conductor of sample 103]
An admittance adjusting layer made of indium tin oxide (ITO) was formed with a thickness of 20 nm on a base material made of PET as follows, and a metal layer made of silver was formed with a thickness of 8 nm on top of this. .

First, a transparent PET substrate is fixed to a substrate holder of a commercially available electron beam evaporation apparatus, indium tin oxide (ITO) is put into a heating boat, and these substrate holder and heating boat are connected to the electron beam evaporation apparatus. Attached to a vacuum chamber. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached to the vacuum chamber of a commercially available vacuum evaporation system.

Next, after reducing the vacuum chamber of the electron beam evaporation apparatus to 4 × 10 ⁻⁴ Pa, the heating boat containing indium tin oxide (ITO) was irradiated with an electron beam and heated, and the deposition rate was 0.1 nm / second. An admittance adjusting layer made of ITO having a thickness of 20 nm was provided on the substrate at a rate of ˜0.2 nm / second.

Next, the base material formed up to the admittance adjustment layer is transferred to a vacuum chamber of a vacuum deposition apparatus while being vacuumed, and the vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, and then a heating boat containing silver is energized and heated. did. As a result, a metal layer made of silver having a thickness of 8 nm is formed at a deposition rate of 0.1 nm / second to 0.2 nm / second, and the transparent conductivity of the sample 103 having a laminated structure of the admittance adjusting layer and the upper metal layer is formed. Got the body.

[Production of transparent conductor of sample 104]
A transparent conductor of Sample 104 was obtained in the same procedure as Sample 103, except that the admittance adjusting layer was composed of titanium oxide (TiO ₂ ).

[Preparation of transparent conductor of sample 105]
As described below, an admittance adjusting layer made of indium tin oxide (ITO) was formed to a thickness of 25 nm on a PET substrate. In addition, the compound Nos. A nitrogen-containing compound consisting of 10 was formed to a thickness of 3 nm to form an organic compound layer. Furthermore, a palladium-containing layer (Pd layer) made of palladium (Pd) is formed as a conductive layer on the organic compound layer with a thickness of 0.1 nm, and a metal layer made of silver is formed thereon with a thickness of 5 nm. did.

First, a base material made of PET is fixed to a base material holder of a commercially available electron beam evaporation apparatus, indium tin oxide (ITO) is placed in a heating boat, and these substrate holder and heating boat are connected to a vacuum chamber of the electron beam evaporation apparatus. Attached to. Next, a palladium (Pd) target was attached to the vacuum chamber of the sputtering apparatus. In addition, a resistance heating boat made of tungsten was combined with the compound No. of the nitrogen-containing compound shown in Table 1 above. 10 was placed and attached to the first vacuum chamber of the vacuum deposition apparatus. Furthermore, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached to the 2nd vacuum chamber of the vacuum evaporation system.

Next, after reducing the vacuum chamber of the electron beam evaporation apparatus to 4 × 10 ⁻⁴ Pa, the heating boat containing ITO is irradiated with an electron beam and heated to evaporate at a deposition rate of 0.1 nm / second to 0.2 nm / second. An admittance adjustment layer made of ITO having a thickness of 25 nm was provided on the substrate in seconds.

Subsequently, the substrate formed up to the admittance adjusting layer was transferred to the first vacuum chamber of the vacuum deposition apparatus while being vacuumed, and the first vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa. The resistance heating boat containing 10 was energized and heated. As a result, the compound No. of nitrogen-containing compound having a deposition rate of 0.1 nm / second to 0.2 nm / second and a thickness of 3 nm was obtained. An organic compound layer consisting of 10 was formed.

Next, the substrate formed up to the organic compound layer is transferred to the vacuum chamber of the sputtering apparatus while being vacuumed, and after the vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, a voltage is applied to the Pd target, A palladium-containing layer made of Pd was provided with a thickness of 0.1 nm.

Next, the base material formed up to the palladium-containing layer is transferred to the second vacuum chamber of the vacuum deposition apparatus while being vacuumed, and after the pressure in the second vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, a resistance heating boat containing silver is added. Heated with electricity. Thus, a metal layer made of silver having a thickness of 5 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.
As a result, a transparent conductor of Sample 105 was obtained in which an admittance adjusting layer, an organic compound layer, a conductive layer composed of a palladium-containing layer and a metal layer were laminated in this order.

[Preparation of transparent conductor of sample 106]
A transparent conductor of Sample 106 was obtained in the same procedure as Sample 105 except that the admittance adjusting layer was composed of titanium oxide (TiO ₂ ) having a thickness of 20 nm.

[Preparation of transparent conductor of sample 107]
A transparent conductor of Sample 107 was obtained in the same procedure as Sample 105 except that the thickness of the metal layer made of silver was 8 nm.

[Preparation of transparent conductor of sample 108]
A transparent conductor of Sample 108 was obtained in the same procedure as Sample 106, except that the thickness of the metal layer made of silver was 8 nm.

[Production of transparent conductor of sample 109]
A transparent conductor of Sample 109 was obtained in the same procedure as Sample 107 except that the admittance adjusting layer was composed of niobium oxide (Nb ₂ O ₅ ).

[Production of transparent conductor of sample 110]
A transparent conductor of Sample 110 was obtained by the same procedure as Sample 109 except that the thickness of the metal layer made of silver was 10 nm.

[Preparation of transparent conductor of sample 111]
A transparent conductor of Sample 111 was obtained in the same procedure as Sample 109 except that the thickness of the metal layer made of silver was 12 nm.

[Production of transparent conductor of sample 112]
A transparent conductor of Sample 112 was obtained in the same procedure as Sample 109 except that the thickness of the metal layer made of silver was 15 nm.

[Production of transparent conductor of sample 113]
As described below, a second admittance adjusting layer made of magnesium fluoride (MgF ₂ ) is formed on a PET substrate with a thickness of 180 nm, and a first portion made of titanium oxide (TiO ₂ ) is formed on the upper part. An admittance adjusting layer was formed with a thickness of 20 nm. In addition, the compound Nos. A nitrogen-containing compound consisting of 10 was formed to a thickness of 3 nm to form an organic compound layer. Further, a palladium-containing layer (Pd layer) made of palladium (Pd) is formed as a conductive layer on the organic compound layer with a thickness of 0.1 nm, and a metal layer made of silver is formed thereon with a thickness of 8 nm. Formed.

First, a base material made of PET is fixed to a base material holder of a commercially available electron beam evaporation apparatus, magnesium fluoride (MgF ₂ ) is put into a heating boat, and these substrate holders and the heating boat are connected to a vacuum of the electron beam evaporation apparatus. Attached to the tank. Further, titanium oxide (TiO ₂ ) was put into a heating boat and attached to the vacuum chamber of the electron beam evaporation apparatus. Next, a palladium (Pd) target was attached to the vacuum chamber of the sputtering apparatus.

Next, a compound No. of nitrogen-containing compounds shown in Table 1 above was placed on a resistance heating boat made of tungsten. 10 was placed and attached to the first vacuum chamber of the vacuum deposition apparatus. Furthermore, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached to the 2nd vacuum chamber of the vacuum evaporation system.

Next, the vacuum chamber of the electron beam evaporation apparatus was depressurized to 4 × 10 ⁻⁴ Pa, and then heated by irradiating an electron beam onto a heating boat containing magnesium fluoride (MgF ₂ ), with a deposition rate of 0.1 nm / A second admittance adjusting layer made of magnesium fluoride having a thickness of 180 nm was provided on the substrate at a rate of from second to 0.2 nm / second.
Further, a heating boat containing titanium oxide (TiO ₂ ) is irradiated with an electron beam and heated to form a titanium oxide having a thickness of 20 nm on the second admittance adjusting layer at a deposition rate of 0.1 nm / sec to 0.2 nm / sec. The 1st admittance adjustment layer which consists of was provided.

Next, the base material formed up to the first admittance adjustment layer is transferred to the vacuum chamber of the sputtering apparatus while being vacuumed, and after the vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, a voltage is applied to the Pd target, A palladium-containing layer made of Pd was provided on the admittance adjusting layer with a thickness of 0.1 nm.

Next, the substrate formed up to the palladium-containing layer is transferred to the second vacuum chamber of the vacuum deposition apparatus while being vacuumed, and after the pressure in the vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing silver is energized. And heated. Thereby, a metal layer made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second. Thereby, the transparent conductor of the sample 113 by which the 2nd admittance adjustment layer, the 1st admittance adjustment layer, the organic compound layer, and the conductive layer which consists of a palladium containing layer and a metal layer were laminated | stacked in this order was obtained.

[Production of transparent conductor of sample 114]
A transparent conductor of Sample 114 was obtained in the same procedure as Sample 113 except that the first admittance adjusting layer was composed of niobium oxide (Nb ₂ O ₅ ).

[Preparation of transparent conductors of samples 115 to 128]
Transparent conductors of Samples 115 to 128 were obtained in the same procedure as Sample 109, except that the organic compound layer was composed of the materials shown in Table 2 below. Each material shown in Table 2 applied to the organic compound layers of Samples 115 to 128 corresponds to the compounds shown in Table 1 above.

[Evaluation of each sample of Example 1]
As the optical characteristics of the transparent conductors of the samples 101 to 128 manufactured by the above method, the determination of optical admittance and the measurement of the absorption rate (average absorption rate, maximum absorption rate, plasmon absorption rate:%) were performed.
For each of the transparent conductors of Samples 101 to 128, the average visible light transmittance (%) and the surface resistance (Ω / sq.) Were measured.
Determination of optical admittance, absorptance (%), average visible light transmittance (%), and surface resistance (Ω / sq.) Were measured as follows.

[How to determine admittance]
The admittance of each interface composing the transparent conductor is measured by the thin film design software Essential Macintosh Ver. It calculated in 9.4.375. Note that the thickness d, refractive index n, and absorption coefficient k of each layer necessary for the calculation are as follows. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

[Measurement method of average absorption rate and maximum absorption rate]
Measuring light (light with a wavelength of 450 nm to 800 nm) is incident on the front surface of the transparent conductor from an angle of 5 °, and the average transmittance and average reflectance of light are measured by Hitachi, Ltd .: spectrophotometer U4100 Was measured. The average absorptance was calculated from a calculation formula of 100− (average transmittance + average reflectance). The measurement light was incident from the substrate side.
Further, transmittance and reflectance at wavelengths of 450 nm to 800 nm were measured by the same method as described above. Then, the absorptance at each wavelength was calculated from a calculation formula of 100− (transmittance + reflectance), and the maximum value obtained was defined as the maximum absorptance.

[Measurement method of plasmon absorption rate]
The plasmon absorption rate of the conductive layer was measured as follows.
First, palladium was formed on a transparent glass substrate at 0.2 s (0.1 nm) on the substrate using a magnetron sputtering apparatus (MSP-1S) manufactured by Vacuum Device Corporation. The average thickness of palladium was calculated from the film formation rate at the manufacturer's nominal value of the sputtering apparatus. Thereafter, 20 nm of silver was formed on the substrate on which palladium was adhered, using a BMC-800T vapor deposition machine manufactured by SYNCHRON. The resistance heating at this time was 210 A, and the film formation rate was 5 Å / s.
The reflectance and transmittance of the obtained conductive layer were measured and calculated as absorptivity = 100− (transmittance + reflectance). Assuming that this conductive layer has no plasmon absorption, the plasmon absorption rate was measured by subtracting from the data obtained by measuring the absorption rate of the conductive layer of the transparent conductor of each sample prepared in the example.
The light transmittance and reflectance were measured with a spectrophotometer U4100 manufactured by Hitachi, Ltd.

[Measurement method of average visible light transmittance]
The light transmittance was measured using a spectrophotometer (U-3300, manufactured by Hitachi, Ltd.), and the average light transmittance was measured in the measurement light (light with a wavelength of 450 nm to 800 nm) using the same base material as the sample as the baseline. .

[Measurement method of surface resistance]
The surface resistance was measured using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Corporation) by a four-terminal four-probe method and a constant current application method.

Table 2 below shows the configurations of Samples 101 to 128 and the measurement results of optical admittance, absorption rate (%), average visible light transmittance (%), and surface resistance (Ω / sq.).

[Evaluation results of Example 1]
In the transparent conductors of Samples 105 to 128 in which the admittance adjusting layer, the organic compound layer, and the conductive layer composed of the palladium-containing layer and the metal layer are formed in this order, each of the absorptances is low, the visible light average transmittance, Good results were also obtained in terms of surface resistance.

In Samples 101 to 104, since the organic compound layer and the palladium-containing layer are not formed, the Ag layer constituting the conductive layer is compared with Samples 105 to 128 in which the organic compound layer and the palladium-containing layer are formed. The uniformity is poor and the light absorption rate of the transparent conductor is large. For this reason, the visible light average transmittance and the surface resistance are also deteriorated.

In the samples 101 to 104, the sample 103 and the sample 104 having the admittance adjusting layer have an improved average visible light transmittance as compared with the sample 101 not having the admittance adjusting layer. From this result, it turns out that the light transmittance of a transparent conductor improves by providing an admittance adjustment layer.

Sample 105 and sample 106 have a metal layer of 5 nm, and sample 107 and sample 108 have a metal layer of 8 nm. Samples 109 to 112 have metal layers of 8 nm, 10 nm, 12 nm, and 15 nm, respectively. When these samples are compared, the surface resistance tends to decrease as the thickness of the metal layer increases.
Furthermore, as the thickness of the metal layer increases, plasmon absorption that depends on the surface shape of the metal layer also decreases.
On the other hand, since the absorption of the conductive layer itself increases as the thickness of the metal layer increases, in samples 109 to 112, the visible light average transmittance of the transparent conductor does not change much.
Therefore, by setting the thickness of the metal layer to 8 nm or more, the film quality of the conductive layer can be improved and the light transmittance of the transparent conductor can be improved. However, if the thickness of the metal layer is increased from 15 nm, the increase in the absorption of the conductive layer itself is larger than the decrease in the plasmon absorption rate. Therefore, the thickness of the metal layer needs to be 15 nm or less.

Sample 113 and sample 114 provided with two admittance adjustment layers have lower average absorptance and improved visible light average transmittance compared to sample 108 and sample 109 provided with the same thickness of conductive layer. . In this manner, by forming a plurality of admittance adjustment layers as in the sample 113 and the sample 114, the optical admittance of the conductor layer can be easily adjusted. And the light transmittance of a transparent conductor can be improved by adjusting preferably the optical admittance of a conductor layer.

Also, samples 115 to 128 having different materials constituting the organic compound layer had the same good results in terms of average visible light transmittance and surface resistance. Therefore, as described in Table 1 above, an organic compound layer formed using a compound having an effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ ≦ [n / M]. And a palladium-containing layer, a highly homogeneous conductive layer is formed. That is, by having the organic compound layer and the palladium-containing layer, the metal layer is formed by single-layer growth type (Frank-van der Merwe: FM type) growth, and the homogeneity of the metal layer is improved. For this reason, the transparent conductor excellent in visible light average transmittance | permeability and surface resistance can be comprised.

Samples 107 to 109 are samples in which the admittance adjusting layers are made of ITO, TiO ₂ , and Nb ₂ O ₅ , respectively. In these samples, the optical admittance x ₁ and x ₂ is increased, the light absorption of the transparent conductive material is reduced. In particular, the sample 109 and the sample 108 having x ₁ and x ₂ of less than 1.8 have a lower absorption factor of the transparent conductor in the sample 109 having x ₁ and x ₂ of 1.8 or more. The sample 109 having the largest x ₁ and x ₂ has the lowest light absorption rate. Similarly, most _{x 1} and _{x 2} is greater sample 109, the largest visible light average transmittance.
Therefore, by increasing the x ₁ and x _2, the light absorption of the transparent conductive material is lowered.

[Fabrication of bottom emission type organic electroluminescence device]
Samples 201 to 228 of bottom emission type organic electroluminescent elements (organic EL elements) provided as transparent anode samples 101 to 128 prepared in Example 1 as anodes under the light emitting functional layer were prepared. A manufacturing procedure will be described with reference to FIG. Table 3 below shows the configuration of the transparent conductor used in the organic electroluminescent elements of Samples 201 to 228. As the samples 201 to 228 of the organic electroluminescent elements, the transparent conductors of the samples 101 to 128 of Example 1 in which the last two digits of the sample number coincide with each other were used.

[Procedure for manufacturing organic electroluminescent elements of samples 201 to 228]
(Formation of transparent conductor)
First, in the preparation of samples 201 to 228, each transparent conductor 52 was formed on the top of a transparent polyethylene terephthalate (PET) base material 51. Each transparent conductor 52 was formed in the same procedure as the samples 101 to 128 of Example 1.

(Hole transport / injection layer formation)
Next, a hole-transporting hole serving as both a hole-injecting layer and a hole-transporting layer made of α-NPD is heated by energizing a heating boat containing α-NPD represented by the following structural formula as a hole-transporting injecting material. The injection layer 53 was formed on the transparent conductor 52. At this time, the deposition rate was 0.1 nm / second to 0.2 nm / second, and the thickness was 20 nm.

(Formation of light emitting layer)
Next, the heating boat containing the host material H4 represented by the following structural formula and the heating boat containing the phosphorescent compound Ir-4 represented by the following structural formula were respectively energized independently, and the host material H4 and phosphorescent light emission were emitted. The light emitting layer 54 made of the photosensitive compound Ir-4 was formed on the hole transport / injection layer 53. At this time, the energization of the heating boat was adjusted so that the deposition rate was the host material H4: phosphorescent compound Ir-4 = 100: 6. Further, the thickness of the light emitting layer 54 was set to 30 nm.

(Formation of hole blocking layer)
Next, a hole-blocking layer 55 made of BAlq was formed on the light-emitting layer 54 by heating a heated boat containing BAlq represented by the following structural formula as a hole-blocking material. At this time, the deposition rate was 0.1 nm / second to 0.2 nm / second, and the thickness was 10 nm.

(Formation of electron transport / injection layer)
Thereafter, as an electron transporting material, a heating boat containing the compound 10 having the structural formula shown above and a heating boat containing potassium fluoride were energized independently, and an electron composed of the compound 10 and potassium fluoride. An electron transport / injection layer 56 serving both as an injection layer and an electron transport layer was formed on the hole blocking layer 55. At this time, the energization of the heating boat was adjusted so that the deposition rate was compound 10: potassium fluoride = 75: 25. The thickness was 30 nm.

(Counter electrode: formation of cathode)
After the above, the base material 51 on which the light emitting functional layer is formed is transferred into the vacuum chamber of the vacuum deposition apparatus, the inside of the second vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, and then attached to the vacuum chamber. The resistance heating boat containing the obtained aluminum was energized and heated. Thus, the counter electrode 57 made of aluminum having a thickness of 100 nm was formed at a deposition rate of 0.3 nm / second. The counter electrode 57 is used as a cathode.
A bottom emission type organic electroluminescence device was formed on the base material 51 by the above method.

(Element sealing)
Thereafter, the organic electroluminescent element is covered with a sealing material made of a glass substrate having a thickness of 300 μm, and an adhesive (sealant) is placed between the transparent sealing material and the substrate 51 in a state of surrounding the organic electroluminescent element. Filled. As the adhesive, an epoxy photocurable adhesive (Luxtrac LC0629B manufactured by Toagosei Co., Ltd.) was used. The adhesive filled between the transparent sealing material and the base material 51 was irradiated with UV light from the glass substrate (transparent sealing material) side, and the adhesive was cured to seal the organic electroluminescent element. .

In the formation of the organic electroluminescent element, a vapor deposition mask is used for forming each layer, and the central 4.5 cm × 4.5 cm of the 5 cm × 5 cm base material 51 is set as the light emitting region, and the width of the entire circumference of the light emitting region is A non-light emitting area of 0.25 cm was provided. In addition, the conductive layer of the transparent conductor 52 serving as the anode and the counter electrode 57 serving as the cathode are insulated from the hole transport / injection layer 53 by the electron transport / injection layer 56 and are formed on the periphery of the substrate 51. The terminal portion was formed in a drawn shape.

As described above, organic electroluminescent elements were provided on the substrate 51, and each light emitting panel of the organic electroluminescent elements of Samples 201 to 228 was obtained by sealing this with a transparent sealing material and an adhesive. In each of these light emitting panels, each color of emitted light h generated in the light emitting layer 54 is taken out from the substrate 51 side.

[Evaluation of each sample of Example 2]
With respect to the organic electroluminescent elements prepared from Samples 201 to 228, the driving voltage (V), the color change (Δxy), and the color rendering properties (Ra) were measured. The results are also shown in Table 3 below.

[Measurement method of drive voltage]
In the measurement of the driving voltage, the voltage when the front luminance at the transparent conductor 52 side (that is, the base material 51 side) of the organic electroluminescent elements of the samples 201 to 228 was 1000 cd / m ² was measured as the driving voltage. . For the measurement of luminance, a spectral radiance meter CS-2000 (manufactured by Konica Minolta Sensing) was used. A smaller value of the obtained drive voltage indicates a more favorable result.

[Measurement method of color change]
In the measurement of the color change, a current of ^2.5 mA / cm ² was applied to the organic electroluminescent elements of the samples 201 to 228, and the chromaticity in the CIE 1931 color system was measured from positions at different angles. At this time, the chromaticity was measured at a position of 0 ° which is a normal direction to the light emitting surface on the transparent conductor 52 side and each position of 45 ° in the vertical horizontal (up, down, left and right) directions. The difference in chromaticity measured at different angles is shown in Table 3 below as color change (Δxy). The color change represents the viewing angle characteristic of chromaticity, and the smaller the value, the better the result.

[Measurement method of color rendering properties]
The color rendering property (Ra) is measured by using a spectral radiance meter CS-2000 (manufactured by Konica Minolta Sensing) and applying a current of ^2.5 mA / cm ² to the organic electroluminescent elements of the samples 201 to 228. The value of was measured. The color rendering property (Ra) indicates that the obtained value is closer to 100 and is a preferable result.

Table 3 below shows the configurations of the samples 201 to 228 and the measurement results of the drive voltage (V), color change (Δxy), and color rendering properties (Ra).

[Evaluation results of Example 2]
In the organic electroluminescent elements of Samples 205 to 228 including the transparent conductor in which the admittance adjusting layer, the organic compound layer, and the conductive layer including the palladium-containing layer and the metal layer are formed in this order, the driving voltage, the color change, and Good results were obtained for all of the color rendering properties.

In the organic electroluminescent elements of Samples 201 to 204, no light was emitted except for Sample 202 in which a metal layer was formed to 12 nm. Also in the sample 202, the measurement result of the color change was low, and a sufficient result could not be obtained. Further, the color rendering properties were lower than those of the organic electroluminescent elements of Samples 205 to 228.

Compared with Sample 205 and Sample 206 in which the metal layer was formed with a thickness of 5 nm, Samples 207 to 212 in which the metal layer was formed with a thickness of 8 nm or more had a low driving voltage and small color change, and good results were obtained.

Further, when the measurement result of the color change is seen, the samples 206 and 208 to 212 using TiO ₂ or Nb ₂ O ₅ as the admittance adjusting layer are compared with the samples 205 and 207 using ITO as the admittance adjusting layer. Good results were obtained. From this result, it is considered preferable to use TiO ₂ or Nb ₂ O ₅ as the admittance adjusting layer.

Furthermore, the sample 213 and the sample 214 provided with two admittance adjusting layers obtained better results in the color change measurement results than the sample 208 and the sample 209 provided with the same thickness of the conductive layer. That is, by forming a plurality of admittance adjusting layers as in the sample 213 and the sample 214, the optical admittance of the conductor layer can be adjusted, and the optical characteristics of the organic electroluminescent element can be improved.

10, 20, 30, 52 ... transparent conductor, 11, 51 ... base material, 12 ... organic compound layer, 13 ... palladium-containing layer, 14 ... metal layer, 15 ... Conductive layer, 21 ... admittance adjustment layer, 31 ... first admittance adjustment layer, 32 ... second admittance adjustment layer, 40 ... organic electroluminescence device, 46 ... light emission functional layer, 46a ..Hole injection layer, 46b... Hole transport layer, 46c, 54... Luminescent layer, 46d... Electron transport layer, 46e. 53 ... Hole transport / injection layer, 55 ... Hole blocking layer, 56 ... Electron transport / injection layer

Claims

An organic compound layer;
A conductive layer provided adjacent to the organic compound layer,
The conductive layer includes a metal layer mainly composed of silver (Ag) and a palladium-containing layer containing palladium (Pd).
The said palladium containing layer is provided in the said organic compound layer side in the said conductive layer. The transparent conductor.
The transparent conductor according to claim 1, wherein the organic compound layer is made of a compound having a Lewis base.
The compound having a Lewis base is a non-shared electron pair that does not participate in aromaticity and is not coordinated to a metal among the non-shared electron pairs that the nitrogen atom (N) or sulfur atom contained in the compound has. 3. The transparent conductor according to claim 2, wherein the effective unshared electron pair content [n / M] when the number is n and the molecular weight is M is 2.0 × 10 −3 ≦ [n / M].
The transparent conductor according to claim 1, wherein the thickness of the metal layer is 3 nm or more and 15 nm or less.
An admittance adjusting layer on the surface of the organic compound layer opposite to the surface on which the conductive layer is formed;
The optical admittance at a wavelength of 570 nm at the interface of the conductive layer on the organic compound layer side is Y 1 = x 1 + iy 1 , and the optical admittance at the interface of the conductive layer on the side opposite to the organic compound layer is Y 2 = x The transparent conductor according to claim 1, wherein at least one of x 1 and x 2 is 1.6 or more when represented by 2 + iy 2 .
The transparent conductor according to claim 5, wherein the admittance adjusting layer contains a dielectric material or an oxide semiconductor material.
The transparent conductor according to claim 5, wherein the conductive layer has a plasmon absorptance of 15% or less over the entire wavelength range of 400 nm to 800 nm.
The transparent conductor according to claim 5, wherein both x 1 and x 2 are 1.6 or more.
The optical and y 1 of the admittance Y 1, wherein a y 2 optical admittance Y 2 is a transparent conductor according to claim 5 satisfies the relationship y 1 × y 2 <0.
The transparent conductor according to claim 5, wherein the admittance adjusting layer contains TiO 2 or Nb 2 O 5 .
The transparent conductor according to claim 5, wherein a refractive index of the admittance adjusting layer is 1.8 or more and 2.5 or less.
The transparent conductor according to claim 5, wherein the admittance adjustment layer includes a first admittance adjustment layer and a second admittance adjustment layer, and the organic compound layer is provided on the first admittance adjustment layer side.
The transparent conductor according to claim 12, wherein a refractive index of the first admittance adjusting layer is 0.2 or more larger than a refractive index of the second admittance adjusting layer.
An electronic device comprising the transparent conductor according to any one of claims 1 to 13.
The electronic device according to claim 14, further comprising a light emitting functional layer on the transparent conductor.