JPWO2013122150A1 - Transparent electrodes and electronic devices - Google Patents

Abstract

A transparent electrode having sufficient conductivity and light transmittance is provided, and further, an electronic device and an organic electroluminescent element whose performance is improved by using the transparent electrode are provided. The transparent electrode 1 has a film thickness of 12 nm or less capable of measuring the sheet resistance, a coverage of 70% or more and 100% or less, and an electrode layer 1b made of silver.

Description

  The present invention relates to a transparent electrode and an electronic device, and more particularly to a transparent electrode having both conductivity and light transmittance, and further to an electronic device using the transparent electrode.

  An organic electroluminescent element (so-called organic EL element) using electroluminescence (hereinafter referred to as EL) of an organic material is a thin-film type completely solid element 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 electrode.

As the transparent electrode, indium tin oxide is _{(SnO 2 -In 2 O 3:} : Indium Tin Oxide ITO) oxide semiconductor-based material such as is commonly used, low by laminating the ITO and silver Studies aiming at resistance have also been made (for example, see Patent Documents 1 and 2 below). However, since ITO uses rare metal indium, the material cost is high, and it is necessary to anneal at about 300 ° C. after film formation in order to reduce resistance. Therefore, a configuration in which a metal material such as silver having high electrical conductivity is thinned, and a configuration in which conductivity is ensured with a thinner film thickness than silver alone by mixing aluminum with silver (for example, the following patent documents) 3).

JP 2002-15623 A Japanese Unexamined Patent Publication No. 2006-164961 JP 2009-151963 A

  However, it has been difficult to achieve both sufficient conductivity and light transmittance even with a transparent electrode composed of silver or aluminum having high electrical conductivity.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a transparent electrode having sufficient conductivity and light transmittance, and to provide an electronic device whose performance is improved by using this transparent electrode.

  The above object of the present invention is achieved by the following configurations.

  1. A transparent electrode having a film thickness of 12 nm or less capable of measuring sheet resistance, a covering ratio of 70% to 100%, and an electrode layer made of silver.

  2. 2. The transparent electrode according to 1 above, wherein the film thickness is 8 nm or less.

  3. 3. The transparent electrode according to 1 or 2, wherein the coverage is 80% or more and 100% or less.

  4). The electronic device which has a transparent electrode of any one of said 1-3.

  5. 5. The electronic device according to 4 above, wherein the electronic device is an organic electroluminescent element.

  The transparent electrode of the present invention configured as described above has practicality as a film for an electrode because the electrode layer constituting the transparent electrode has a film thickness of 12 nm or less capable of measuring sheet resistance. While securing, the absorption component or the reflection component is kept low. In particular, the electrode layer has a coverage of 70% or more and 100% or less, so that the sheet resistance can be reliably measured and the conductivity is ensured even though the electrode layer is an extremely thin film of 12 nm or less as described above. It will be.

  As a result of the above, the transparent electrode having such an electrode layer has a thin electrode layer that functions substantially as an electrode, while ensuring light transmission and ensuring conductivity. Therefore, both the improvement of conductivity and the improvement of light transmittance are achieved.

  As described above, according to the present invention, it is possible to achieve both improvement in conductivity and light transmission in the transparent electrode, and improvement in performance of an electronic device using the transparent electrode. It becomes possible.

It is a plane schematic diagram for demonstrating the structure of the transparent electrode of this invention. It is a cross-sectional schematic diagram which shows the structure of the transparent electrode of this invention. It is a section lineblock diagram showing the 1st example of an organic electroluminescent element using a transparent electrode of the present invention. It is a cross-sectional block diagram which shows the 2nd example of the organic electroluminescent element using the transparent electrode of this invention. It is a cross-sectional block diagram which shows the 3rd example of the organic electroluminescent element using the transparent electrode of this invention. It is a cross-sectional block diagram which shows the 4th example of the organic electroluminescent element using the transparent electrode of this invention. It is a cross-sectional block diagram of the illuminating device which enlarged the light emission surface using the organic electroluminescent element. It is the SEM image of the transparent electrode of the sample 1-1 produced in Example 1, and the processed image which image-processed this. It is the SEM image of the transparent electrode of sample 1-4 produced in Example 1, and the processed image which image-processed this. It is the SEM image of the transparent electrode of the sample 1-11 produced in Example 1, and the process image which image-processed this. It is the SEM image of the transparent electrode of sample 1-13 produced in Example 1, and the processed image which image-processed this. It is a graph which shows the relationship between effective action energy (DELTA) Eef and sheet resistance in the transparent electrode produced in Example 2. FIG. FIG. 5 is a cross-sectional configuration diagram illustrating an organic electroluminescent element produced in Example 3.

Hereinafter, embodiments of the present invention will be described in the following order based on the drawings.
1. 1. Transparent electrode 2. Use of transparent electrode First example of organic electroluminescence device (top emission type)
4). Second example of organic electroluminescence device (bottom emission type)
5). Third example of organic electroluminescence device (double-sided light emission type)
6). Fourth example of organic electroluminescence device (reverse stacking configuration)
7). Use of organic electroluminescence device8. Lighting device-1
9. Illumination device-2

<< 1. Transparent electrode >>
FIG. 1 is a schematic plan view for explaining the configuration of the transparent electrode of the present invention. FIG. 2 is a schematic cross-sectional view showing one structural example of the transparent electrode of the present invention. As shown in these drawings, the transparent electrode 1 has an electrode layer 1b provided adjacent to the nitrogen-containing layer 1a, and only the electrode layer 1b may be the transparent electrode 1, and the nitrogen-containing layer 1a A laminated structure with the electrode layer 1b may be a transparent electrode. Such a transparent electrode 1 is provided in the order of, for example, a nitrogen-containing layer 1a and an electrode layer 1b on the base 11. Among these, the electrode layer 1b constituting the electrode portion in the transparent electrode 1 is characterized in that it has a predetermined film thickness and film formation state, as will be described in detail later. Further, the nitrogen-containing layer 1a provided adjacent to the electrode layer 1b is a layer formed using a material having a specific relationship with the electrode material constituting the electrode layer 1b, for example.

  Below, a detailed structure is demonstrated in order of the base material 11 in which the electrode layer 1b which comprises the transparent electrode 1 of such a laminated structure, the nitrogen containing layer 1a, and the transparent electrode 1 are provided. In addition, the transparency of the transparent electrode 1 of the present invention means that the light transmittance at a wavelength of 550 nm is 50% or more.

<Electrode layer 1b>
The electrode layer 1b is a layer formed using a conductive material, for example, a layer formed on the nitrogen-containing layer 1a. This electrode layer 1b has a film thickness of 12 nm or less capable of measuring the sheet resistance. The electrode layer 1b has a two-dimensional continuity in the in-plane direction of the conductive material constituting the electrode layer 1b by setting the film thickness so that the sheet resistance can be measured. As a practicality, it is ensured. Moreover, the electrode layer 1b has a film thickness of 12 nm or less, so that the absorption component or reflection component in the electrode layer 1b is kept low, and the light transmittance of the transparent electrode 1 is ensured.

  The electrode layer 1b has a coverage of 70% or more and 100% or less. Here, since the electrode layer 1b is an extremely thin film having a thickness of 12 nm or less, depending on the film formation state, as shown in the schematic plan view of FIG. . Even in such a case, an electrode having an occupation ratio of the conductive material excluding the opening a on the surface of the electrode layer 1b of 70% or more and 100% or less, that is, a covering ratio of 70% or more and 100% or less is used. It will be used as the layer 1b. The coverage is preferably 80% or more and 100% or less. That is, the ratio of the opening a on the surface of the electrode layer 1b is 0% or more and 30% or less, and preferably 20% or less. The electrode layer 1b is most preferably a completely continuous film having no opening a. In this case, the proportion of the conductive material on the surface of the electrode layer 1b is 100%, and the coverage is 100%.

  Such a coverage is obtained by processing a surface image observed using, for example, a scanning electron microscope, and obtaining the coverage of the conductive material in the processed image. The scanning electron microscope is a microscope suitable for observing a surface region having a width of about 500 nm × 500 nm on the surface of the electrode layer 1b, for example.

  Note that the image processing is performed, for example, by binarizing the contrast of a secondary electron image or a reflected electron image obtained by a scanning electron microscope. Then, as shown in FIG. 1, the coverage ratio of the conductive material in the electrode layer 1b is obtained with the binarized contrast black display portion as the opening a and the white display portion as the coating surface with the conductive material.

  The conductive material constituting the electrode layer 1b as described above is silver (Ag) or an alloy mainly composed of silver. Examples thereof include silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd). ), Silver palladium copper (AgPdCu), silver indium (AgIn), and the like.

  As a method for forming the electrode layer 1b as described above, 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, or the like. And a method using a dry process such as a method. Of these, the vapor deposition method is preferably applied. In addition, the electrode layer 1b is formed on the nitrogen-containing layer 1a, so that the electrode layer 1b is sufficiently conductive even without high-temperature annealing after the film formation. The film may be subjected to a high temperature annealing treatment after the film.

  Furthermore, the electrode layer 1b 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.

<Nitrogen-containing layer 1a>
As shown in the schematic cross-sectional view of FIG. 2, the nitrogen-containing layer 1a is a layer provided as a base for the electrode layer 1b. The nitrogen-containing layer 1a is a layer made of, for example, an organic material, and an electrode layer 1b is formed thereon by single-layer growth type (FW-type) film growth. It may be composed of materials. As an example, when the electrode layer 1b is made of silver or an alloy containing silver as a main component, the nitrogen-containing layer 1a is exemplified by a configuration using an organic material containing nitrogen atoms (N). Hereinafter, the detailed structure of the nitrogen-containing layer 1a in the case where the electrode layer 1b is composed of silver or an alloy containing silver as a main component will be described.

  That is, the nitrogen-containing layer 1a is a compound having a specific relationship with silver (Ag), which is the main material constituting the electrode layer 1b, among compounds containing a heterocycle having a nitrogen atom (N) as a hetero atom. It is the layer comprised using. Here, the effective action energy ΔEef represented by the following formula (1) is defined as the energy that interacts between the compound and silver. And this effective action energy (DELTA) Eef comprises the nitrogen-containing layer 1a using the compound which has the specific relationship which satisfy | fills following formula (2).

  The number of nitrogen atoms in the compound that stably binds to silver [n] is selected from the nitrogen atoms contained in the compound as the specific nitrogen atom only from the nitrogen atoms that stably bind to silver Is the number counted. The nitrogen atoms to be selected are all nitrogen atoms contained in the compound, and are not limited to the nitrogen atoms constituting the heterocyclic ring. The selection of a specific nitrogen atom out of all the nitrogen atoms contained in such a compound is, for example, the bond distance [r (Ag · Ag · N)], or the angle between the nitrogen atom and silver, that is, the dihedral angle [D], relative to the ring containing the nitrogen atom in the compound, is performed as follows. The molecular orbital calculation is performed using, for example, Gaussian 03 (Gaussian, Inc., Wallingford, CT, 2003).

  First, when the bond distance [r (Ag · N)] is used as an index, considering the steric structure of each compound, the distance at which the nitrogen atom and silver are stably bonded in the compound is expressed as “stable bond distance”. ”Is set. Then, for each nitrogen atom contained in the compound, a bond distance [r (Ag · N)] is calculated using a molecular orbital calculation method. A nitrogen atom having a calculated bond distance [r (Ag · N)] close to the “stable bond distance” is selected as a specific nitrogen atom. Such selection of a nitrogen atom is applied to a compound containing many nitrogen atoms constituting a heterocyclic ring and a compound containing many nitrogen atoms not constituting a heterocyclic ring.

  When the dihedral angle [D] is used as an index, the dihedral angle [D] described above is calculated using a molecular orbital calculation method. Then, a nitrogen atom whose calculated dihedral angle [D] satisfies D <10 degrees is selected as a specific nitrogen atom. Such selection of a nitrogen atom is applied to a compound containing a large number of nitrogen atoms constituting a heterocyclic ring.

  The interaction energy [ΔE] between silver (Ag) and nitrogen (N) in the compound can be calculated by a molecular orbital calculation method, and the mutual energy between nitrogen and silver selected as described above. The energy of action.

  Further, the surface area [s] is calculated for the optimized structure using Tencube / WM (manufactured by Tencube Co., Ltd.).

  The effective action energy ΔEef defined as described above is more preferably within a range satisfying the following formula (3).

  Moreover, as a heterocycle having a nitrogen atom (N) contained in the compound constituting the nitrogen-containing layer 1a as a heteroatom, aziridine, azirine, azetidine, azeto, azolidine, azole, azinane, pyridine, azepan, azepine, imidazole, pyrazole Oxazole, thiazole, imidazoline, pyrazine, morpholine, thiazine, indole, isoindole, benzimidazole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzo-C-cinnoline, porphyrin, chlorin, choline, etc. Can be mentioned.

  Moreover, as a compound which has a heterocyclic ring which used the nitrogen atom as the hetero atom, the compound preferably used is, for example, a compound represented by the following general formula (1) or a compound represented by the following general formula (2). Is done. The nitrogen-containing layer 1a constituting the transparent electrode 1 of the present invention is a compound represented by the general formula (1) or the general formula (2) among the compounds applicable to the formula (1) or the formula (2) described above. Is selected and used.

  In the formula of the general formula (1), Y5 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof. E51 to E66 and E71 to E88 each represent -C (R3) = or -N =, and R3 represents a hydrogen atom or a substituent. However, at least one of E71 to E79 and at least one of E80 to E88 represents -N =. n3 and n4 represent an integer of 0 to 4, but n3 + n4 is an integer of 2 or more.

  In the general formula (1), examples of the arylene group represented by Y5 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 (1), examples of the heteroarylene group represented by Y5 include a carbazole ring, a carboline ring, a diazacarbazole ring (also referred to as a monoazacarboline ring, and one of the 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 comprising an arylene group, a heteroarylene group or a combination thereof represented by Y5, 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 (1), examples of the substituent represented by R3 of —C (R3) ═ represented by E51 to E66 and E71 to E88 are alkyl groups (for example, methyl group, ethyl group, propyl group). Group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group etc.), alkenyl group ( For example, vinyl group, allyl group, etc.), alkynyl group (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon group (aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group Mesityl, tolyl, xylyl, naphthyl, anthryl, azulenyl, acenaphthenyl, fluore Group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group), aromatic heterocyclic group (for example, 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 (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), a phthalazinyl group, etc.) , Heterocyclic groups (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy groups (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group) Group), cycloalkoxy (Eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy 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 group (eg phenylthio group, naphthylthio group etc.), alkoxycarbonyl group (eg methyloxycarbonyl group, ethyloxycarbonyl group) Butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), Rufamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthyl) Aminosulfonyl 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) Butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonyl) Amino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino 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 Nyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl 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 (for example, phenylsulfonyl group, naphthylsulfonyl group, 2 -Pyridylsulfonyl group, etc.), amino group (for example, 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 atom (eg fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (For example, fluoro Til group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, Phenyldiethylsilyl group, etc.), phosphoric acid ester groups (eg, dihexyl phosphoryl group, etc.), phosphite ester groups (eg, diphenylphosphinyl group, etc.), phosphono groups, and the like.

  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.

  In general formula (1), it is preferable that 6 or more of E51 to E58 and 6 or more of E59 to E66 are each represented by -C (R3) =.

  In General formula (1), it is preferable that at least 1 of E75-E79 and at least 1 of E84-E88 represent -N =.

  Furthermore, in General formula (1), it is preferable that any one of E75-E79 and any one of E84-E88 represent -N =.

  Moreover, in General formula (1), it is mentioned as a preferable aspect that E71-E74 and E80-E83 are each represented by -C (R3) =.

  Furthermore, in the compound represented by the general formula (1), it is preferable that E53 is represented by -C (R3) = and R3 represents a linking site, and E61 is also represented by -C (R3) =. And R3 preferably represents a linking site.

  Further, E75 and E84 are preferably represented by -N =, and E71 to E74 and E80 to E83 are each preferably represented by -C (R3) =.

Moreover, the compound represented by following General formula (2) is used as another example of the compound which comprises the nitrogen containing layer 1a.

  In the general formula (2), at least one of T11 and T12 is a nitrogen atom, at least one of T21 to T25 is a nitrogen atom, and at least one of T31 to T35 is Nitrogen atom.

  In the general formula (2), R represents a substituent. As an example of a substituent, the same thing as R3 of General formula (1) is mentioned. These substituents may be further substituted with the above substituents.

  When the nitrogen-containing layer 1a as described above is formed on the substrate 11, the film forming method includes a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, Examples include a method using a dry process such as a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, or the like. Of these, the vapor deposition method is preferably applied.

[Specific examples of compounds]
Although the specific example (1-112) of the compound which comprises the nitrogen containing layer 1a below is shown, it is not limited to these. In addition, the compound which is not contained in the said General formula (1) and General formula (2) here is illustrated here. In addition, the nitrogen-containing layer 1a constituting the transparent electrode 1 of the present invention is selected and used from among the compounds (1-112) exemplified below, a compound corresponding to the above formula (1) or formula (2). It is done.

[Examples of compound synthesis]
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 And mixed 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 was performed using toluene = 4: 1 to 3: 1), and Intermediate 1 was obtained with 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 under air, 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. Next, 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).

  After distilling off the solvent from the purified product under reduced pressure, the residue was dissolved again in dichloromethane and washed three times with water. 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%.

<Substrate 11>
Examples of the substrate 11 on which the transparent electrode 1 as described above is formed include, but are not limited to, glass and plastic. Further, the substrate 11 may be transparent or opaque. When the transparent electrode 1 of the present invention is used in an electronic device that extracts light from the substrate 11 side, the substrate 11 is preferably transparent. Examples of the transparent substrate 11 that is preferably used include glass, quartz, and a transparent resin film.

  Examples of the glass include silica glass, soda-lime silica glass, lead glass, borosilicate glass, and alkali-free glass. From the viewpoints of adhesion, durability, and smoothness with the nitrogen-containing layer 1a, the surface of these glass materials is subjected to physical treatment such as polishing, a coating made of an inorganic material or an organic material, if necessary, A hybrid film combining these films is formed.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and 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 polyarylate, 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) of 0.01 g / (measured by a method according to JIS-K-7129-1992. 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 a 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 high barrier film is preferable.

  The material for forming the barrier film as described above may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like is used. be able to. 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 weighting. A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method described in JP-A-2004-68143 is particularly preferable.

  On the other hand, when the base material 11 is opaque, for example, a metal substrate such as aluminum or stainless steel, a film, an opaque resin substrate, a ceramic substrate, or the like can be used.

  Note that the transparent electrode 1 having the electrode layer 1b as described above may have the upper part of the electrode layer 1b covered with a protective film or may be laminated with another conductive layer. 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 electrode layer 1b. Moreover, it is good also as a structure which provided the layer as needed also in the lower part of the nitrogen containing layer 1a, ie, between the nitrogen containing layer 1a and the base material 11. FIG. Further, in the above embodiment, the transparent electrode 1 has been described as a laminated structure of the nitrogen-containing layer 1a and the electrode layer 1b. However, the transparent electrode 1 may have a single-layer structure including only the electrode layer 1b.

<Effect of transparent electrode 1>
The transparent electrode 1 as described above has practicality as a film for an electrode because the electrode layer 1b constituting the transparent electrode 1 has a film thickness of 12 nm or less capable of measuring the sheet resistance. Also, the light absorption component or the reflection component is suppressed to a low level. In particular, since the electrode layer 1b has a coverage of 70% or more and 100% or less, the electrode layer 1b has a conductivity capable of reliably measuring the sheet resistance even though it is an extremely thin film of 12 nm or less as described above. It will be a thing. Moreover, if the coverage is 80% or more and 100% or less, the sheet resistance can be further suppressed to a low value.

  As a result, in the transparent electrode 1 having such an electrode layer 1b, the electrode layer 1b that substantially functions as an electrode has a thin film thickness, while ensuring light transmission, Since it is ensured, it becomes possible to achieve both improvement in conductivity and improvement in light transmission.

  Further, such a transparent electrode 1 is low in cost because it does not use indium (In), which is a rare metal, and has excellent long-term reliability because it does not use a chemically unstable material such as ZnO. Yes.

  Further, such an electrode layer 1b is made of silver or an alloy containing silver as a main component, and is provided adjacent to the nitrogen-containing layer 1a formed using a compound having a nitrogen atom. When the electrode layer 1b is formed on the nitrogen-containing layer 1a, silver atoms constituting the electrode layer 1b interact with the compound containing nitrogen atoms constituting the nitrogen-containing layer 1a, and silver The diffusion distance of atoms on the surface of the nitrogen-containing layer 1a is reduced, and a continuous silver film is formed. Therefore, in general, a silver thin film that is easily isolated in an island shape by film growth of a nuclear growth type (Volume-Weber: VW type) is a single-layer growth type (Frank-van der Merwe: FW type) film growth. As a result, a film is formed. Therefore, the electrode layer 1b having a uniform film thickness can be obtained even though the film thickness is small.

  In particular, the effective action energy ΔEef shown in the above formula (1) is defined as the energy that interacts between the compound that constitutes the nitrogen-containing layer 1a and the silver that constitutes the electrode layer 1b. The nitrogen-containing layer 1a was configured using a compound satisfying −0.4 ≦ ΔEef ≦ −0.10. This makes it possible to form the nitrogen-containing layer 1a using a compound that can reliably obtain the effect of “suppressing the aggregation of silver” as described above. This is confirmed from the fact that an electrode layer 1b capable of measuring sheet resistance is formed on such a nitrogen-containing layer 1a even though it is an extremely thin film, as will be described in detail in a later example. It was done.

≪2. Applications of transparent electrodes >>
The transparent electrode 1 having the above-described configuration can be used for various electronic devices. Examples of electronic devices include organic electroluminescent elements, LEDs (light emitting diodes), liquid crystal elements, solar cells, touch panels, etc. As electrode members that require light transmission in these electronic devices, A transparent electrode 1 can be used.
Hereinafter, as an example of the application, an embodiment of an organic electroluminescent element using transparent electrodes as an anode and a cathode will be described.

≪3. First example of organic electroluminescence device (top emission type) >>
<Configuration of organic electroluminescent element EL-1>
FIG. 3 is a cross-sectional configuration diagram showing a first example of an organic electroluminescent element using the transparent electrode 1 described above as an example of the electronic device of the present invention. The configuration of the organic electroluminescent element will be described below based on this figure.

  The organic electroluminescent element EL-1 shown in FIG. 3 is provided on the substrate 13, and in order from the substrate 13 side, the light-emitting functional layer 3 configured using the counter electrode 5-1, an organic material, and the like, and a transparent The electrode 1 is laminated in this order. The organic electroluminescent element EL-1 is characterized in that the transparent electrode 1 of the present invention described above is used as the transparent electrode 1. For this reason, the organic electroluminescent element EL-1 is configured as a top emission type in which generated light (hereinafter referred to as emitted light h) is extracted from at least the side opposite to the substrate 13.

  Further, the overall layer structure of the organic electroluminescent element EL-1 is not limited and may be a general layer structure. Here, the transparent electrode 1 is disposed on the cathode (ie, cathode) side, and the electrode layer 1b mainly functions as the cathode, while the counter electrode 5-1 functions as the anode (ie, anode).

  In this case, for example, the light emitting functional layer 3 is formed by laminating [hole injection layer 3a / hole transport layer 3b / light emitting layer 3c / electron transport layer 3d / electron injection layer 3e] in this order from the counter electrode 5-1 side which is an anode. Of these, it is essential to have the light emitting layer 3c composed of at least an organic material. The hole injection layer 3a and the hole transport layer 3b may be provided as a hole transport / injection layer. The electron transport layer 3d and the electron injection layer 3e may be provided as an electron transport / injection layer. Among these light emitting functional layers 3, for example, the electron injection layer 3e may be made of an inorganic material.

  Furthermore, in the transparent electrode 1 provided as a cathode, the nitrogen-containing layer 1a may also serve as an electron injection layer or may serve as an electron transport / injection layer.

  In addition to these layers, the light-emitting functional layer 3 may be laminated with a hole blocking layer, an electron blocking layer, and the like as necessary. Furthermore, the light emitting layer 3c has each color light emitting layer for generating emitted light in each wavelength region, and each color light emitting layer may be laminated through a non-light emitting intermediate layer to form a light emitting layer unit. good. The intermediate layer may function as a hole blocking layer and an electron blocking layer. Further, the counter electrode 5-1 as an anode may also have a laminated structure as necessary. In such a configuration, only a portion where the light emitting functional layer 3 is sandwiched between the transparent electrode 1 and the counter electrode 5-1 becomes a light emitting region in the organic electroluminescent element EL-1.

  In the layer configuration as described above, the auxiliary electrode 15 may be provided in contact with the electrode layer 1 b of the transparent electrode 1 for the purpose of reducing the resistance of the transparent electrode 1.

  The organic electroluminescent element EL-1 having the above-described configuration is a transparent sealing material 17 described later on the substrate 13 for the purpose of preventing deterioration of the light emitting functional layer 3 formed using an organic material or the like. It is sealed. The transparent sealing material 17 is fixed to the substrate 13 side through an adhesive 19. However, the terminal portions of the transparent electrode 1 and the counter electrode 5-1 are provided on the substrate 13 so as to be exposed from the transparent sealing material 17 while being insulated from each other by the light emitting functional layer 3. To do.

  Hereinafter, the details of the main layers for constituting the organic electroluminescent element EL-1 described above will be described in addition to the substrate 13, the transparent electrode 1, the counter electrode 5-1, the light emitting layer 3c of the light emitting functional layer 3, and the light emitting functional layer 3. The layer, the auxiliary electrode 15, and the transparent sealing material 17 will be described in this order. Thereafter, a method for producing the organic electroluminescent element EL-1 will be described.

[Substrate 13]
The substrate 13 is the same as the base material on which the transparent electrode 1 of the present invention described above is provided. However, when the organic electroluminescent element EL-1 is a double-sided light emitting type that also takes out the emitted light h from the counter electrode 5-1, the transparent material having light transmittance is selected from the base material 11 and used. It is done.

[Transparent electrode 1 (cathode side)]
The transparent electrode 1 is the transparent electrode 1 described above, and has a configuration in which a nitrogen-containing layer 1a and an electrode layer 1b are sequentially formed from the light emitting functional layer 3 side. Here, in particular, the electrode layer 1b of the present invention constituting the transparent electrode 1 is a substantial cathode. Further, in the organic electroluminescent element EL-1 of the present embodiment, a nitrogen-containing layer 1a made of an organic material is disposed between the light emitting functional layer 3 and the electrode layer 1b used as a substantial cathode. Become. For this reason, the nitrogen-containing layer 1 a of the transparent electrode 1 in the present embodiment is also regarded as a layer constituting a part of the light emitting functional layer 3. Such a nitrogen-containing layer 1a is preferably constituted by using a material having an electron transporting property or an electron injecting property among materials satisfying the above-described formula (1) or formula (2). Further, such a nitrogen-containing layer 1a may be configured using a material satisfying the formula (1) or the formula (2) among the materials exemplified as an electron transport material hereinafter. In this case, since the nitrogen-containing layer 1a is regarded as the light emitting functional layer 3, it can be said that the transparent electrode 1 has a single-layer structure composed of only the electrode layer 1b.

[Counter electrode 5-1 (anode)]
The counter electrode 5-1 is an electrode film that functions as an anode for supplying holes to the light emitting functional layer 3, 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 5-1 can be produced by forming a thin film of these conductive materials by a method such as vapor deposition or sputtering. The sheet resistance as the counter electrode 5-1 is several hundred Ω / sq. The following is preferable, and the film thickness is usually selected in the range of 5 nm to 5 μm, preferably 5 nm to 200 nm.

  If the organic electroluminescent element EL-1 is a double-sided light emitting type that takes out the emitted light h from the counter electrode 5-1 side, a conductive material having good light transmittance among the conductive materials described above is used. The counter electrode 5-1 may be configured by selection.

[Light emitting layer 3c]
The light emitting layer 3c used in the present invention contains, for example, a phosphorescent compound as a light emitting material.

  The light emitting layer 3c is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer 3d and holes injected from the hole transport layer 3b, and the light emitting portion is the light emitting layer 3c. Even within the layer, it may be the interface between the light emitting layer 3c and the adjacent layer.

  There is no restriction | limiting in particular in the structure as such a light emitting layer 3c, if the light emitting material contained 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 3c.

  The total thickness of the light emitting layer 3c is preferably in the range of 1 to 100 nm, and more preferably 1 to 30 nm because a lower driving voltage can be obtained. In addition, the sum total of the film thickness of the light emitting layer 3c is a film thickness also including the said intermediate | middle layer, when a nonluminous intermediate | middle layer exists between the light emitting layers 3c.

  In the case of the light emitting layer 3c 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, more preferably adjusted to a range of 1 to 20 nm. . When the plurality of stacked light emitting layers correspond to blue, green, and red light emitting colors, there is no particular limitation on the relationship between the film thicknesses of the blue, green, and red light emitting layers.

  The light emitting layer 3c as described above is formed by forming a light emitting material or a host compound 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. be able to.

  The light emitting layer 3c 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 3c.

  As a structure of the light emitting layer 3c, it is preferable to contain a host compound (also referred to as a light emitting host or the like) and a light emitting material (also referred to as a light emitting dopant compound) and to emit light from the light emitting material.

(Host compound)
As the host compound contained in the light emitting layer 3c, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. More preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in the light emitting layer 3c.

  As a host compound, a well-known host compound may be used independently, or multiple types may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the efficiency of the organic electroluminescent element EL-1 can be increased. 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 hole transporting ability and an electron transporting ability, preventing an increase in emission wavelength, and having a high Tg (glass transition temperature) compound is preferable. The glass transition point (Tg) here is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).

  Although the specific example (H1-H79) of the host compound which can be used by this invention below is shown, it is not limited to these. In the host compounds H68 to H79, x and y represent the ratio of the random copolymer. The ratio can be, for example, x: y = 1: 10.

  As specific examples of known host compounds, compounds described in the following documents may be used. For example, Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860 Gazette, 2002-334787 gazette, 2002-15871 gazette, 2002-334788 gazette, 2002-43056 gazette, 2002-334789 gazette, 2002-75645 gazette, 2002-338579 gazette. 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. 2002-302516, 2002-305083, 2002-305084, 2002-308837, and the like.

(Luminescent material)
As a light-emitting material that can be used in the present invention, a phosphorescent compound (also referred to as a phosphorescent compound or a phosphorescent material) can be given.

  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 phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, when using a phosphorescent compound in the present invention, the above 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 the phosphorescent compound. 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 compounds used for the light emitting layer of a general organic electroluminescence device, but preferably contains a metal of group 8 to 10 in the periodic table of elements. More preferred are iridium compounds, more preferred are iridium compounds, osmium compounds, platinum compounds (platinum complex compounds), and rare earth complexes, and most preferred are iridium compounds.

  In the present invention, at least one light emitting layer 3c may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the light emitting layer 3c varies in the thickness direction of the light emitting layer 3c. It may be.

  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 3c.

(Compound represented by the general formula (3))
The compound (phosphorescent compound) contained in the light emitting layer 3c is preferably a compound represented by the following general formula (3).

  The phosphorescent compound represented by the general formula (3) (also referred to as a phosphorescent metal complex) is preferably contained as a light emitting dopant in the light emitting layer 3c of the organic electroluminescent element EL-1. However, it may be contained in a light emitting functional layer other than the light emitting layer 3c.

  In the general formula (3), P and Q each represent a carbon atom or a nitrogen atom, and A1 represents an atomic group that forms an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with P—C. A2 represents an atomic group which forms an aromatic heterocycle with QN. P1-L1-P2 represents a bidentate ligand, and P1 and P2 each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L1 represents an atomic group that forms a bidentate ligand together with P1 and P2. j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 is 2 or 3. M1 represents a group 8-10 transition metal element in the periodic table.

  In general formula (3), P and Q each represent a carbon atom or a nitrogen atom.

  In the general formula (3), the aromatic hydrocarbon ring that A1 forms with P—C includes a 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 ring, Examples include a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring.

  These rings may further have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88 in the general formula (1).

  In the general formula (3), the aromatic heterocycle formed by A1 together with P—C 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, a 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, azacarbazole A ring etc. are mentioned.

  Here, the azacarbazole ring refers to one in which one or more carbon atoms of the benzene ring constituting the carbazole ring are replaced with a nitrogen atom.

  These rings may further have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88 in the general formula (1).

  In the general formula (3), examples of the aromatic heterocycle formed by A2 together with QN include an oxazole ring, an oxadiazole ring, an oxatriazole ring, an isoxazole ring, a tetrazole ring, a thiadiazole ring, a thiatriazole ring, Examples include a thiazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, an imidazole ring, a pyrazole ring, and a triazole ring.

  These rings may further have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88 in the general formula (1).

  In the general formula (3), P1-L1-P2 represents a bidentate ligand, and P1 and P2 each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L1 represents an atomic group that forms a bidentate ligand together with P1 and P2.

  Examples of the bidentate ligand represented by P1-L1-P2 include phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, acetylacetone, and picolinic acid.

  In general formula (3), j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, j1 + j2 represents 2 or 3, and j2 is preferably 0.

  In General Formula (3), M1 is a transition metal element of Group 8 to Group 10 (also referred to simply as a transition metal) in the periodic table of elements. Among these, iridium is preferable.

(Compound represented by the general formula (4))
Among the compounds represented by the general formula (3), a compound represented by the following general formula (4) is more preferable.

  In the general formula (4), Z represents a hydrocarbon ring group or a heterocyclic group. P and Q each represent a carbon atom or a nitrogen atom, and A1 represents an atomic group that forms an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with PC. A3 represents -C (R01) = C (R02)-, -N = C (R02)-, -C (R01) = N- or -N = N-, and each of R01 and R02 represents a hydrogen atom or a substituent. Represents a group. P1-L1-P2 represents a bidentate ligand, and P1 and P2 each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L1 represents an atomic group that forms a bidentate ligand together with P1 and P2. j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 is 2 or 3. M1 represents a group 8-10 transition metal element in the periodic table.

  In the general formula (4), examples of the hydrocarbon ring group represented by Z include a non-aromatic hydrocarbon ring group and an aromatic hydrocarbon ring group, and examples of the non-aromatic hydrocarbon ring group include a cyclopropyl group. , Cyclopentyl group, cyclohexyl group and the like. These groups may be unsubstituted or have a substituent described later.

  Examples of the aromatic hydrocarbon ring group (also referred to as aromatic hydrocarbon group, aryl group, etc.) include, 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 and the like.

  These groups may be unsubstituted or may have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88 in the general formula (1).

  In the general formula (4), examples of the heterocyclic group represented by Z include a non-aromatic heterocyclic group and an aromatic heterocyclic group. Examples of the non-aromatic heterocyclic group include an epoxy ring and an aziridine group. Ring, thiirane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ε-caprolactone ring, ε- Caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane ring, tetrahydrothiopyran ring, thiomorpholine Ring, thiomorpholine-1,1-dioxide And groups derived from a ring, a pyranose ring, a diazabicyclo [2,2,2] -octane ring, and the like.

  These groups may be unsubstituted or may have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88 in the general formula (1).

  Examples of the aromatic heterocyclic group include pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl). Group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group , Benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl Group, pyridazinyl group, triazinyl group, key Zoriniru group, phthalazinyl group, and the like.

  These groups may be unsubstituted or may have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88 in the general formula (1).

  Preferably, the group represented by Z is an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

  In the general formula (4), the aromatic hydrocarbon ring that A1 forms with P—C includes a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysene ring, and a 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 ring, picene ring , Pyrene ring, pyranthrene ring, anthraanthrene ring and the like.

  These rings may further have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88 in the general formula (1).

  In the general formula (4), the aromatic heterocycle formed by A1 together with PC includes furan ring, thiophene ring, oxazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzo Imidazole 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, carboline ring, And azacarbazole ring.

  Here, the azacarbazole ring refers to one in which one or more carbon atoms of the benzene ring constituting the carbazole ring are replaced with a nitrogen atom.

  These rings may further have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88 in the general formula (1).

  In -C (R01) = C (R02)-, -N = C (R02)-, and -C (R01) = N- represented by A3 in the general formula (4), each represented by R01 and R02 In general formula (1), the substituent is synonymous with the substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88.

  In the general formula (4), examples of the bidentate ligand represented by P1-L1-P2 include phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabole, acetylacetone, and picolinic acid. .

  J1 represents an integer of 1 to 3, and j2 represents an integer of 0 to 2, j1 + j2 represents 2 or 3, and j2 is preferably 0.

  In General Formula (4), Group 8 to Group 10 transition metal elements in the periodic table of elements represented by M1 (also simply referred to as transition metals) in General Formula (3) are represented in the periodic table of elements represented by M1. It is synonymous with the transition metal element of Group 8-10.

(Compound represented by the general formula (5))
One preferred embodiment of the compound represented by the general formula (4) is a compound represented by the following general formula (5).

In the general formula (5), R ₀₃ represents a substituent, R ₀₄ represents a hydrogen atom or a substituent, and a plurality of R ₀₄ may be bonded to each other to form a ring. n01 represents an integer of 1 to 4. R ₀₅ represents a hydrogen atom or a substituent, and a plurality of R ₀₅ may be bonded to each other to form a ring. n02 represents an integer of 1 to 2. R ₀₆ represents a hydrogen atom or a substituent, and may combine with each other to form a ring. n03 represents an integer of 1 to 4. Z1 represents an atomic group necessary for forming a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle together with C—C. Z2 represents an atomic group necessary for forming a hydrocarbon ring group or a heterocyclic group. P1-L1-P2 represents a bidentate ligand, and P1 and P2 each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L1 represents an atomic group that forms a bidentate ligand together with P1 and P2. j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 is 2 or 3. M1 represents a group 8-10 transition metal element in the periodic table. R ₀₃ and R ₀₆ , R ₀₄ and R _06, and R ₀₅ and R ₀₆ may be bonded to each other to form a ring.

In the general formula (5), each of the substituents represented by R ₀₃ , R ₀₄ , R ₀₅ , and R ₀₆ is represented by —C (R 3) represented by E51 to E66 and E71 to E88, respectively, in the general formula (1). ) = Synonymous with the substituent represented by R3.

  In the general formula (5), examples of the 6-membered aromatic hydrocarbon ring formed by Z1 together with C—C include a benzene ring.

  These rings may further have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88 in the general formula (1).

  In the general formula (5), examples of the 5- or 6-membered aromatic heterocycle formed by Z1 together with C—C include an oxazole ring, an oxadiazole ring, an oxatriazole ring, an isoxazole ring, a tetrazole ring, and a thiadiazole. And a ring, a thiatriazole ring, an isothiazole ring, a thiophene ring, a furan ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, an imidazole ring, a pyrazole ring, and a triazole ring.

  These rings may further have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88 in the general formula (1).

  In the general formula (5), examples of the hydrocarbon ring group represented by Z2 include a non-aromatic hydrocarbon ring group and an aromatic hydrocarbon ring group, and examples of the non-aromatic hydrocarbon ring group include a cyclopropyl group. , Cyclopentyl group, cyclohexyl group and the like. These groups may be unsubstituted or have a substituent described later.

  Examples of the aromatic hydrocarbon ring group (also referred to as aromatic hydrocarbon group, aryl group, etc.) include, 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 and the like. These groups may be unsubstituted or may have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88, respectively, in the general formula (1).

  In the general formula (5), examples of the heterocyclic group represented by Z2 include a non-aromatic heterocyclic group and an aromatic heterocyclic group. Examples of the non-aromatic heterocyclic group include an epoxy ring and an aziridine group. Ring, thiirane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ε-caprolactone ring, ε- Caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane ring, tetrahydrothiopyran ring, thiomorpholine Ring, thiomorpholine-1,1-dioxy And groups derived from a dodo ring, a pyranose ring, a diazabicyclo [2,2,2] -octane ring, and the like. These groups may be unsubstituted or may have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88 in the general formula (1). .

  Examples of the aromatic heterocyclic group include pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl). Group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group , Benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl Group, pyridazinyl group, triazinyl group, key Zoriniru group, phthalazinyl group, and the like.

  These rings may be unsubstituted, and may further have a substituent represented by R3 of -C (R3) = represented by E51 to E66 and E71 to E88 in the general formula (1). .

  In the general formula (5), the group formed by Z1 and Z2 is preferably a benzene ring.

  In the general formula (5), the bidentate ligand represented by P1-L1-P2 has the same meaning as the bidentate ligand represented by P1-L1-P2 in the general formula (3). .

  In general formula (5), the transition metal element of group 8 to group 10 in the periodic table of elements represented by M1 is the transition of group 8 to group 10 in the periodic table of elements represented by M1 in general formula (3). Synonymous with metal element.

  The phosphorescent compound can be appropriately selected from known materials used for the light emitting layer 3c of the organic electroluminescent element EL-1.

  The phosphorescent compound according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex compound). Rare earth complexes, most preferably iridium compounds.

  Specific examples (Pt-1 to Pt-3, A-1, Ir-1 to Ir-45) of the phosphorescent compound according to the present invention are shown below, but the present invention is not limited thereto. In these compounds, m and n represent the number of repetitions.

  The phosphorescent compound (also referred to as a phosphorescent metal complex) is described in, for example, Organic Letters, vol. 3, no. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) , New Journal of Chemistry. , Vol. 26, 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and synthesis by applying methods such as references described in these documents. it can.

(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 3a, electron injection layer 3e]
The injection layer is a layer provided between the electrode and the light emitting layer 3c 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 the 2nd volume of “S. Co., Ltd.”, which includes a hole injection layer 3a and an electron injection layer 3e.

  The injection layer can be provided as necessary. The hole injection layer 3a may be present between the anode and the light emitting layer 3c or the hole transport layer 3b, and the electron injection layer 3e may be present between the cathode and the light emitting layer 3c or the electron transport layer 3d.

  The details of the hole injection layer 3a 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 3e 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 3e of the present invention is desirably a very thin film, and the film thickness is preferably in the range of 1 nm to 10 μm although it depends on the material.

[Hole transport layer 3b]
The hole transport layer 3b is made of a hole transport material having a function of transporting holes, and in a broad sense, the hole injection layer 3a and the electron blocking layer are also included in the hole transport layer 3b. The hole transport layer 3b can be provided as a single layer or a plurality of layers.

  The hole transport material has any one 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.

  Although the above-mentioned thing can be used as a positive hole transport material, It is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styryl amine compound, especially 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 ' − (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, as well as two of those described in US Pat. No. 5,061,569 Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.

  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, 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.

  JP-A-11-251067, J. Org. Huang et. al. , Applied Physics Letters, 80 (2002), p. A so-called p-type hole transport material as described in 139 can also be used. In the present invention, it is preferable to use these materials because a light-emitting element with higher efficiency can be obtained.

  The hole transport layer 3b 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. Although there is no restriction | limiting in particular about the film thickness of the positive hole transport layer 3b, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The hole transport layer 3b may have a single layer structure composed of one or more of the above materials.

  Also, the p-type can be enhanced by doping impurities into the material of the hole transport layer 3b. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  Thus, it is preferable to increase the p property of the hole transport layer 3b because an element with lower power consumption can be manufactured.

[Electron transport layer 3d]
The electron transport layer 3d is made of a material having a function of transporting electrons. In a broad sense, the electron injection layer 3e and a hole blocking layer (not shown) are also included in the electron transport layer 3d. The electron transport layer 3d can be provided as a single layer structure or a multi-layer structure.

  As an electron transport material (also serving as a hole blocking material) that constitutes a layer portion adjacent to the light emitting layer 3c in the electron transport layer 3d having a single layer structure and the electron transport layer 3d 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 3c. 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 an 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 3d. 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 the material of the electron transport layer 3d.

  In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with alkyl groups or sulfonic acid groups can be preferably used as the material for the electron transport layer 3d. Further, a distyrylpyrazine derivative exemplified also as a material of the light emitting layer 3c can be used as a material of the electron transport layer 3d, and similarly to the hole injection layer 3a and the hole transport layer 3b, n-type -Si, n An inorganic semiconductor such as type-SiC can also be used as the material of the electron transport layer 3d.

  The electron transport layer 3d 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. Although there is no restriction | limiting in particular about the film thickness of 3 d of electron carrying layers, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer 3d may have a single layer structure composed of one or more of the above materials.

  In addition, the electron transport layer 3d can be doped with impurities to increase the n property. 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 3d 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 3d is increased, an element with lower power consumption can be manufactured.

  As the material (electron transporting compound) of the electron transport layer 3d, a compound represented by the following general formula (6) can be preferably used.

(Ar1) n1-Y1 General formula (6)

  In the formula (6), n1 represents an integer of 1 or more, Y1 represents a substituent when n1 is 1, and represents a single bond or an n1-valent linking group when n1 is 2 or more. Ar1 represents a group represented by the general formula (A) described later. When n1 is 2 or more, a plurality of Ar1s may be the same or different. However, the compound represented by the general formula (6) has at least two condensed aromatic heterocycles in which three or more rings are condensed in the molecule.

  In the general formula (6), examples of the substituent represented by Y1 are respectively represented by E51 to E66 and E71 to E88 in the general formula (1) shown as the compounds constituting the nitrogen-containing layer 1a of the transparent electrode 1. It is synonymous with the substituent represented by R3 of -C (R3) =.

  Specific examples of the n1-valent linking group represented by Y1 in the general formula (6) include a divalent linking group, a trivalent linking group, and a tetravalent linking group.

  In the general formula (6), as the divalent linking group represented by Y1, an alkylene group (for example, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group, 2,2,4-trimethylhexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, cyclohexylene group (for example, 1,6-cyclohexanediyl group, etc.), Cyclopentylene group (for example, 1,5-cyclopentanediyl group and the like), alkenylene group (for example, vinylene group, propenylene group, butenylene group, pentenylene group, 1-methylvinylene group, 1-methylpropenylene group, 2-methylpropenylene group, 1-methylpentenylene group, 3-methyl Ntenylene group, 1-ethylvinylene group, 1-ethylpropenylene group, 1-ethylbutenylene group, 3-ethylbutenylene group, etc.), alkynylene group (for example, ethynylene group, 1-propynylene group, 1-butynylene group, 1-pentynylene group) 1-hexynylene group, 2-butynylene group, 2-pentynylene group, 1-methylethynylene group, 3-methyl-1-propynylene group, 3-methyl-1-butynylene group, etc.), arylene group (for example, o-phenylene group) , P-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group, biphenyldiyl group (for example, [1,1′-biphenyl] -4,4′-diyl group, 3, 3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terf Nildiyl group, quaterphenyldiyl group, kinkphenyldiyl group, sexiphenyldiyl group, septiphenyldiyl group, octiphenyldiyl group, nobiphenyldiyl group, deciphenyldiyl group, etc.), heteroarylene group (for example, carbazole) Ring, carboline ring, diazacarbazole ring (also called monoazacarboline ring, which shows a ring structure in which one of carbon atoms constituting carboline ring is replaced by nitrogen atom), triazole ring, pyrrole ring, pyridine ring, pyrazine Ring, quinoxaline ring, thiophene ring, oxadiazole ring, dibenzofuran ring, dibenzothiophene ring, divalent group derived from the group consisting of indole ring, etc.), chalcogen atom such as oxygen and sulfur, 3 or more rings Groups derived from condensed aromatic heterocycles formed by condensation (this Here, the condensed aromatic heterocyclic ring formed by condensing three or more rings is preferably an aromatic heterocyclic ring containing a hetero atom selected from N, O and S as an element constituting the condensed ring. Specifically, acridine ring, benzoquinoline ring, carbazole ring, phenazine ring, phenanthridine ring, phenanthroline ring, carboline ring, cyclazine ring, kindrin ring, tepenidine ring, quinindrin ring, triphenodithia Gin ring, triphenodioxazine ring, phenanthrazine ring, anthrazine ring, perimidine ring, diazacarbazole ring (representing any one of carbon atoms constituting carboline ring replaced by nitrogen atom), phenanthroline ring, dibenzofuran Ring, dibenzothiophene ring, naphthofuran ring, naphthothiophene ring, Nzodifuran ring, benzodithiophene ring, naphthodifuran ring, naphthodithiophene ring, anthrafuran ring, anthradifuran ring, anthrathiophene ring, anthradithiophene ring, thianthrene ring, phenoxathiin ring, thiophanthrene ring (naphthothiophene ring) ) Etc.).

  In the general formula (6), examples of the trivalent linking group represented by Y1 include ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, and octanetriyl. Group, nonanetriyl group, decanetriyl group, undecanetriyl group, dodecanetriyl group, cyclohexanetriyl group, cyclopentanetriyl group, benzenetriyl group, naphthalenetriyl group, pyridinetriyl group, carbazoletriyl group, etc. Can be mentioned.

  In the general formula (6), the tetravalent linking group represented by Y1 is a group in which one trivalent group is further added to the above trivalent group, and examples thereof include a propanediylidene group and 1,3-propane. Diyl-2-ylidene group, butanediylidene group, pentanediylidene group, hexanediylidene group, heptanediylidene group, octanediylidene group, nonanediylidene group, decandiylidene group, undecandiylidene group, dodecandiylidene group, cyclohexanediylidene group , Cyclopentanediylidene group, benzenetetrayl group, naphthalenetetrayl group, pyridinetetrayl group, carbazoletetrayl group and the like.

  The divalent linking group, the trivalent linking group, and the tetravalent linking group are each further represented by -51 (E3) to E66 and E71 to E88 in the general formula (1). May have a substituent represented by R3.

  As a preferred embodiment of the compound represented by the general formula (6), Y1 preferably represents a group derived from a condensed aromatic heterocycle formed by condensation of three or more rings, and the three or more rings. As the condensed aromatic heterocyclic ring formed by condensing, a dibenzofuran ring or a dibenzothiophene ring is preferable. Further, n1 is preferably 2 or more.

  Furthermore, the compound represented by the general formula (6) has at least two condensed aromatic heterocycles obtained by condensing the above three or more rings in the molecule.

  When Y1 represents an n1-valent linking group, Y1 is preferably non-conjugated in order to keep the triplet excitation energy of the compound represented by the general formula (6) high, and further, Tg (glass transition In view of improving the point, also referred to as glass transition temperature, it is preferably composed of an aromatic ring (aromatic hydrocarbon ring + aromatic heterocycle).

  Here, the term “non-conjugated” means that the linking group cannot be expressed by repeating a single bond (also referred to as a single bond) and a double bond, or the conjugation between aromatic rings constituting the linking group is sterically cleaved. Means.

[Group represented by general formula (A)]
Ar1 in the general formula (6) represents a group represented by the following general formula (A).

  In the formula, X represents —N (R) —, —O—, —S— or —Si (R) (R ′) —, and E1 to E8 represent —C (R1) ═ or —N═. R, R ′ and R1 each represent a hydrogen atom, a substituent or a linking site with Y1. * Represents a linking site with Y1. Y2 represents a simple bond or a divalent linking group. Y3 and Y4 each represent a group derived from a 5-membered or 6-membered aromatic ring, and at least one represents a group derived from an aromatic heterocycle containing a nitrogen atom as a ring constituent atom. n2 represents an integer of 1 to 4.

  Here, in —N (R) — or —Si (R) (R ′) — represented by X in the general formula (A), and —C (R1) = represented by E1 to E8, The substituents represented by R, R ′ and R1 have the same meaning as the substituents represented by R3 of —C (R3) ═ represented by E51 to E66 and E71 to E88 in the general formula (1), respectively. is there.

  In the general formula (A), the divalent linking group represented by Y2 has the same meaning as the divalent linking group represented by Y1 in the general formula (6).

  Further, in the general formula (A), as the 5-membered or 6-membered aromatic ring used for forming a group derived from a 5-membered or 6-membered aromatic ring represented by Y3 and Y4, respectively, Oxazole ring, thiophene ring, furan ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, diazine ring, triazine ring, imidazole ring, isoxazole ring, pyrazole ring, triazole ring and the like.

  Further, at least one of the groups derived from a 5-membered or 6-membered aromatic ring represented by Y3 and Y4 represents a group derived from an aromatic heterocycle containing a nitrogen atom as a ring constituent atom, Examples of the aromatic heterocycle containing a nitrogen atom as the ring constituent atom include an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a diazine ring, a triazine ring, an imidazole ring, an isoxazole ring, a pyrazole ring, Examples include a triazole ring.

(Preferred embodiment of the group represented by Y3)
In the general formula (A), the group represented by Y3 is preferably a group derived from the above 6-membered aromatic ring, and more preferably a group derived from a benzene ring.

(Preferred embodiment of the group represented by Y4)
In the general formula (A), the group represented by Y4 is preferably a group derived from the 6-membered aromatic ring, more preferably an aromatic heterocycle containing a nitrogen atom as a ring constituent atom. Particularly preferably, Y4 is a group derived from a pyridine ring.

(Preferred embodiment of the group represented by the general formula (A))
A preferable embodiment of the group represented by the general formula (A) is represented by any one of the following general formulas (A-1), (A-2), (A-3), or (A-4). Groups.

  In the general formula (A-1), X represents —N (R) —, —O—, —S— or —Si (R) (R ′) —, and E1 to E8 represent —C (R1 ) = Or -N =, and R, R 'and R1 each represent a hydrogen atom, a substituent, or a linking site with Y1. Y2 represents a simple bond or a divalent linking group. E11 to E20 represent -C (R2) = or -N =, and at least one represents -N =. R2 represents a hydrogen atom, a substituent or a linking site. However, at least one of E11 and E12 represents -C (R2) =, and R2 represents a linking site. n2 represents an integer of 1 to 4. * Represents a linking site with Y1 in the general formula (6).

  In the general formula (A-2), X represents —N (R) —, —O—, —S— or —Si (R) (R ′) —, and E1 to E8 represent —C (R1 ) = Or -N =, and R, R 'and R1 each represent a hydrogen atom, a substituent, or a linking site with Y1. Y2 represents a simple bond or a divalent linking group. E21 to E25 represent -C (R2) = or -N =, and E26 to E30 represent -C (R2) =, -N =, -O-, -S- or -Si (R3) (R4)-. And at least one of E21 to E30 represents -N =. R2 represents a hydrogen atom, a substituent or a linking site, and R3 and R4 represent a hydrogen atom or a substituent. However, at least one of E21 or E22 represents -C (R2) =, and R2 represents a linking site. n2 represents an integer of 1 to 4. * Represents a linking site with Y1 in the general formula (6).

  In the general formula (A-3), X represents —N (R) —, —O—, —S— or —Si (R) (R ′) —, and E1 to E8 represent —C (R1 ) = Or -N =, and R, R 'and R1 each represent a hydrogen atom, a substituent, or a linking site with Y1. Y2 represents a simple bond or a divalent linking group. E31 to E35 represent -C (R2) =, -N =, -O-, -S- or -Si (R3) (R4)-, and E36 to E40 represent -C (R2) = or -N =. And at least one of E31 to E40 represents -N =. R2 represents a hydrogen atom, a substituent or a linking site, and R3 and R4 represent a hydrogen atom or a substituent. However, at least one of E32 or E33 is represented by -C (R2) =, and R2 represents a linking site. n2 represents an integer of 1 to 4. * Represents a linking site with Y1 in the general formula (6).

  In the general formula (A-4), X represents —N (R) —, —O—, —S— or —Si (R) (R ′) —, and E1 to E8 represent —C (R1 ) = Or -N =, and R, R 'and R1 each represent a hydrogen atom, a substituent, or a linking site with Y1. Y2 represents a simple bond or a divalent linking group. E41 to E50 represent -C (R2) =, -N =, -O-, -S-, or -Si (R3) (R4)-, and at least one represents -N =. R2 represents a hydrogen atom, a substituent or a linking site, and R3 and R4 represent a hydrogen atom or a substituent. However, at least one of E42 or E43 is represented by -C (R2) =, and R2 represents a linking site. n2 represents an integer of 1 to 4. * Represents a linking site with Y1 in the general formula (6).

  Hereinafter, the group represented by any one of the general formulas (A-1) to (A-4) will be described.

  In —N (R) — or —Si (R) (R ′) — represented by X in any of the groups represented by formulas (A-1) to (A-4), E1 to In -C (R1) = represented by E8, the substituents represented by R, R 'and R1 are each represented by -C (R3 represented by E51 to E66 and E71 to E88 in the general formula (1), respectively. ) = Synonymous with the substituent represented by R3.

  In any of the groups represented by the general formulas (A-1) to (A-4), the divalent linking group represented by Y2 is a divalent group represented by Y1 in the general formula (6). It is synonymous with the linking group.

  E11 to E20 of the general formula (A-1), E21 to E30 of the general formula (A-2), E31 to E40 of the general formula (A-3), E41 to E50 of the general formula (A-4), respectively. The substituent represented by R2 of —C (R2) ═ represented by the substitution represented by R3 of —C (R3) ═ represented by E51 to E66 and E71 to E88 in the general formula (1), respectively. Synonymous with group.

  Next, a further preferred embodiment of the compound represented by the general formula (6) according to the present invention will be described.

[Compound represented by the general formula (7)]
In the present invention, among the compounds represented by the general formula (6), a compound represented by the following general formula (7) is preferable. The general formula (7) includes the general formula (1) shown as a compound constituting the nitrogen-containing layer 1a of the transparent electrode 1. Hereinafter, the compound represented by the general formula (7) will be described.

  In the general formula (7), Y5 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof. E51 to E66 each represent -C (R3) = or -N =, and R3 represents a hydrogen atom or a substituent. Y6 to Y9 each represents a group derived from an aromatic hydrocarbon ring or a group derived from an aromatic heterocycle, and at least one of Y6 or Y7 and at least one of Y8 or Y9 is an aromatic group containing an N atom. Represents a group derived from a group heterocycle. n3 and n4 represent an integer of 0 to 4, but n3 + n4 is an integer of 2 or more.

  Y5 in General formula (7) is synonymous with Y5 in General formula (1).

  E51 to E66 in the general formula (7) have the same meanings as E51 to E66 in the general formula (1).

  In the general formula (7), as groups represented by E51 to E66, 6 or more of E51 to E58 and 6 or more of E59 to E66 are each represented by -C (R3) =. It is preferable.

  In the general formula (7), Y6 to Y9 are each an aromatic hydrocarbon ring used for forming a group derived from an aromatic hydrocarbon ring, such as a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an 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 ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene ring, and the like.

  Furthermore, the aromatic hydrocarbon ring may have a substituent represented by R3 of -C (R3) = represented by E51 to E66 in the general formula (1).

  In the general formula (7), Y6 to Y9 are each an aromatic heterocycle used for forming a group derived from an aromatic heterocycle, for example, a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, or a pyridine ring. , Pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, indazole ring, benzimidazole ring, benzothiazole ring, benzoxazole Ring, quinoxaline ring, quinazoline ring, cinnoline ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, carbazole ring, carboline ring, diazacarbazole ring (one of the carbon atoms constituting the carboline ring is further substituted with a nitrogen atom) Shows the ring that is) It is below.

  Furthermore, the aromatic hydrocarbon ring may have a substituent represented by R3 of -C (R3) = represented by E51 to E66 in the general formula (1).

  In the general formula (7), an aromatic heterocycle containing an N atom used for forming a group derived from an aromatic heterocycle containing an N atom represented by at least one of Y6 or Y7 and at least one of Y8 or Y9. Examples of the ring include oxazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring. , Indazole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, carbazole ring, carboline ring, diazacarbazole ring (carboline ring) Composing charcoal It shows a ring in which one atom is further substituted with a nitrogen atom), and the like.

  In general formula (7), the groups represented by Y7 and Y9 each preferably represent a group derived from a pyridine ring.

  In the general formula (7), the groups represented by Y6 and Y8 each preferably represent a group derived from a benzene ring.

  Among the compounds represented by the general formula (7) as described above, the compound represented by the general formula (1) shown as the compound constituting the nitrogen-containing layer 1a of the transparent electrode 1 is exemplified as a more preferable embodiment. The

  As specific examples of the compound represented by the general formula (6), (7), or the general formula (1), the compounds (1-112) exemplified above are shown.

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

  The hole blocking layer has the function of the electron transport layer 3d 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 3d mentioned later can be used as a hole-blocking layer based on this invention as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer 3c.

  On the other hand, the electron blocking layer has the function of the hole transport layer 3b 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 3b mentioned later can be used as an electron blocking layer as needed. The film thickness of the hole blocking layer according to the present invention is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

[Auxiliary electrode 15]
The auxiliary electrode 15 is provided for the purpose of reducing the resistance of the transparent electrode 1, and is provided in contact with the electrode layer 1 b of the transparent electrode 1. The material forming the auxiliary electrode 15 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 17a. Examples of the method for forming the auxiliary electrode 15 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 15 is preferably 50 μm or less from the viewpoint of the aperture ratio for extracting light, and the thickness of the auxiliary electrode 15 is preferably 1 μm or more from the viewpoint of conductivity.

[Transparent encapsulant 17]
The transparent sealing material 17 covers the organic electroluminescent element EL-1 and is a plate-shaped (film-shaped) sealing member that is fixed to the substrate 13 by the adhesive 19. It may be a sealing film. The surface of the transparent sealing material 17 serves as a light extraction surface 17a for extracting the emitted light h of the organic electroluminescent element EL-1. Such a transparent sealing material 17 is provided in a state of covering at least the light emitting functional layer 3 in a state in which the terminal portions of the transparent electrode 1 and the counter electrode 5-1 in the organic electroluminescent element EL-1 are exposed. Further, an electrode may be provided on the transparent sealing material 17 so that the electrode is electrically connected to the terminal portions of the transparent electrode 1 and the counter electrode 5-1 of the organic electroluminescent element EL-1.

  Specific examples of the plate-like (film-like) transparent sealing material 17 include a glass substrate and a polymer substrate. 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 transparent sealing material 17 in which a polymer substrate is formed into a thin film can be preferably used.

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

  The above substrate material may be processed into a concave plate shape and used as the transparent sealing material 17. In this case, the above-described substrate member is subjected to processing such as sand blasting or chemical etching to form a concave shape.

  An adhesive 19 for fixing the plate-like transparent sealing material 17 to the substrate 13 side seals the organic electroluminescent element EL-1 sandwiched between the transparent sealing material 17 and the substrate 13. Used as a sealing agent to stop. Specifically, such an adhesive 19 is a photocuring and thermosetting adhesive having a reactive vinyl group of an acrylic acid-based oligomer, a methacrylic acid-based oligomer, a moisture-curing type such as 2-cyanoacrylic acid ester, or the like. Can be mentioned.

  Examples of such an adhesive 19 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 organic electroluminescent element EL-1 may deteriorate with heat processing. Therefore, the adhesive 19 is preferably one that can be adhesively cured from room temperature to 80 ° C. Further, a desiccant may be dispersed in the adhesive 19.

  Application | coating of the adhesive agent 19 to the adhesion part of the transparent sealing material 17 and the board | substrate 13 may use a commercially available dispenser, and may print like screen printing.

  In addition, when a gap is formed between the plate-shaped transparent sealing material 17, the substrate 13, and the adhesive 19, this gap has an inert gas such as nitrogen or argon or fluoride in the gas phase and the liquid phase. It is preferable to inject an inert liquid such as hydrocarbon 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 film is used as the transparent sealing material 17, the light emitting functional layer 3 in the organic electroluminescent element EL-1 is completely covered, and the transparent electrode 1 and the counter electrode 5-1 in the organic electroluminescent element EL-1 are covered. A sealing film is provided on the substrate 13 with the terminal portions thereof exposed.

  Such a sealing film is configured using 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 3 in the organic electroluminescent element EL-1, 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. Furthermore, in order to improve the brittleness of the sealing film, a laminated structure may be formed by using a film made of an organic material together with a film made of these inorganic materials.

  The method for forming these films 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 film, protective plate]
Although illustration is omitted here, a protective film or a protective plate may be provided between the substrate 13 and the organic electroluminescent element EL and the transparent sealing material 17. This protective film or protective plate is for mechanically protecting the organic electroluminescent element EL, and in particular, when the transparent sealing material 17 is a sealing film, it is mechanical for the organic electroluminescent element EL. Since protection is not sufficient, it is preferable to provide such a protective film or protective plate.

  As the protective film or protective plate as described above, a glass plate, a polymer plate, a polymer film thinner than this, a metal plate, a metal film thinner than this, or a polymer material film or metal material film is applied. Among these, it is particularly preferable to use a polymer film because it is light and thin.

[Method for Fabricating Organic Electroluminescent Device]
Here, as an example, a method of manufacturing the organic electroluminescent element EL-1 shown in FIG. 3 will be described.

  First, the counter electrode 5-1 to be an anode is formed on the substrate 13 by an appropriate film forming method such as a vapor deposition method or a sputtering method.

Next, a hole injection layer 3a, a hole transport layer 3b, a light emitting layer 3c, an electron transport layer 3d, and an electron injection layer 3e are formed in this order on this, and the light emitting functional layer 3 is formed. The film formation of each of these layers includes spin coating, casting, ink jet, vapor deposition, sputtering, printing, etc., but it is easy to obtain a uniform film and it is difficult to generate pinholes. A vacuum deposition method or a spin coating method is particularly preferable. Further, different film forming methods may be applied for each layer. When employing a vapor deposition method for forming each of these layers, the vapor deposition conditions vary depending on the type of compound used, etc., but generally the boat heating temperature is 50 ° C. to 450 ° C., the degree of vacuum is 10 ⁻⁶ Pa to 10 ⁻² Pa, It is desirable to select each condition as appropriate within the range of 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, a nitrogen-containing layer 1a made of a compound containing a nitrogen atom is formed so as to have a thickness of 1 μm or less, preferably 10 nm to 100 nm. Thereafter, an electrode layer 1b made of silver (or an alloy containing silver as a main component) is formed so as to have a film thickness of 4 nm to 12 nm, and the transparent electrode 1 on the cathode side is manufactured. These nitrogen-containing layer 1a and electrode layer 1b can be formed by spin coating, casting, ink jet, vapor deposition, sputtering, printing, etc., but it is easy to obtain a homogeneous film and pinholes are generated. Vacuum vapor deposition is particularly preferred from the standpoint of difficulty.

  In particular, in the formation of the electrode layer 1b, a pattern is formed in a shape in which a terminal portion is drawn from the upper side of the light emitting functional layer 3 to the periphery of the substrate 13 while maintaining the insulating state with respect to the counter electrode 5-1 by the light emitting functional layer 3. To do. In addition, before and after the formation of the electrode layer 1b, a pattern of the auxiliary electrode 15 is formed as necessary. Thereby, organic electroluminescent element EL-1 is obtained. Thereafter, a transparent sealing material 17 covering at least the light emitting functional layer 3 is provided in a state where the terminal portions of the transparent electrode 1 and the counter electrode 5-1 in the organic electroluminescent element EL-1 are exposed. At this time, the adhesive 19 is used to adhere the transparent sealing material 17 to the substrate 13 side, and the organic electroluminescent element EL-1 is sealed between the transparent sealing material 17 and the substrate 13.

  Thus, a desired organic electroluminescent element EL-1 is obtained on the substrate 13. In the production of such an organic electroluminescent element EL-1, it is preferable that the light emitting functional layer 3 is consistently produced from the counter electrode 5-1 by one evacuation, but the substrate 13 is removed from the vacuum atmosphere in the middle. You may take out and perform a different film-forming method. 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 electroluminescent element EL-1 obtained in this way, the counter electrode 5-1 as an anode has a positive polarity and the electrode layer 1b as a cathode has a negative polarity. When a voltage of about 2 V to 40 V is applied, light emission can be observed. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

<Effect of organic electroluminescent element EL-1>
The organic electroluminescent element EL-1 described above uses the electrode layer 1b of the transparent electrode 1 having both conductivity and light transmittance of the present invention as a cathode, and emits light on the nitrogen-containing layer 1a side of the transparent electrode 1. In this configuration, the functional layer 3 and the counter electrode 5-1 serving as the anode are provided in this order. For this reason, a sufficient voltage is applied between the electrode layer 1b and the counter electrode 5-1 to realize high-intensity light emission in the organic electroluminescent element EL-1, while the emitted light h from the transparent electrode 1 side is emitted. It is possible to increase the luminance by improving the extraction efficiency. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance.

<< 4. Second example of organic electroluminescence device (bottom emission type) >>
<Configuration of organic electroluminescent element>
FIG. 4 is a cross-sectional configuration diagram illustrating a second example of an organic electroluminescent element using the above-described transparent electrode as an example of the electronic device of the present invention. The organic electroluminescent element EL-2 of the second example shown in this figure is different from the organic electroluminescent element EL-1 of the first example described with reference to FIG. 3 in that the transparent electrode 1 is provided on the transparent substrate 13 ′. The light emitting functional layer 3 and the counter electrode 5-2 are laminated in this order on the upper portion. Hereinafter, the detailed description of the same components as those in the first example will be omitted, and the characteristic configuration of the organic electroluminescence element EL-2 in the second example will be described.

  The organic electroluminescent element EL-2 shown in FIG. 4 is provided on the transparent substrate 13 ′, and in order from the transparent substrate 13 ′ side, the transparent electrode 1 having the electrode layer 1b serving as an anode, the light emitting functional layer 3, and A counter electrode 5-2 serving as a cathode is laminated. Of these, the transparent electrode 1 is characterized in that the transparent electrode 1 of the present invention described above is used. For this reason, the organic electroluminescent element EL-2 is configured as a bottom emission type in which the emitted light h is extracted from at least the transparent substrate 13 'side.

  The overall layer structure of the organic electroluminescent element EL-2 is not limited, but may be a general layer structure as in the first example. As an example in the case of the second example, a hole injection layer 3a / a hole transport layer 3b / a light emitting layer 3c / an electron transport layer 3d / an electron injection layer are formed on the electrode layer 1b of the transparent electrode 1 functioning as an anode. 3e is laminated in this order, and a configuration in which a counter electrode 5-2 serving as a cathode is further laminated thereon is exemplified. However, it is essential to have at least the light emitting layer 3c configured using an organic material. The electron transport layer 3d also serves as the electron injection layer 3e, and may be provided as an electron transport layer 3d having electron injection properties.

  In addition to these layers, the light-emitting functional layer 3 employs various configurations as necessary, as described in the first example, and a hole blocking layer or an electron whose illustration is omitted here. A blocking layer may be provided. In the above configuration, only the portion where the light emitting functional layer 3 is sandwiched between the transparent electrode 1 and the counter electrode 5-2 becomes the light emitting region in the organic electroluminescent element EL-2. It is.

  Further, in the organic electroluminescent element EL-2 of the present embodiment, the light emitting functional layer 3 is directly provided on the electrode layer 1b which functions substantially as an anode in the transparent electrode 1. Therefore, the nitrogen-containing layer 1a of the electrode layer 1b may be configured using a material that satisfies the above-described formula (1) or (2), and it is not necessary to use a material having an electron transporting property or an electron injecting property. . Furthermore, as long as the transparent electrode 1 includes the electrode layer 1b having the above-described configuration, the transparent electrode 1 may be configured by only the electrode layer 1b without the nitrogen-containing layer 1a.

  In the layer configuration as described above, the auxiliary electrode 15 may be provided in contact with the electrode layer 1b of the transparent electrode 1 for the purpose of reducing the resistance of the transparent electrode 1 in the first example. It is the same.

Further, the counter electrode 5-2 provided as a cathode above the light emitting functional layer 3 is made of a metal, an alloy, an organic or inorganic conductive compound, and a mixture thereof. Specific examples include metals such as gold (Au), oxide semiconductors such as copper iodide (CuI), ITO, ZnO, TiO ₂ , and SnO ₂ .

  The counter electrode 5-2 as described above can be produced by forming a thin film of these conductive materials by a method such as vapor deposition or sputtering. The sheet resistance as the counter electrode 5-2 is several hundred Ω / sq. The following is preferable, and the film thickness is usually selected in the range of 5 nm to 5 μm, preferably 5 nm to 200 nm.

  Further, the sealing material 17 ′ for sealing the bottom emission type organic electroluminescent element EL- 2 does not need to have light transmittance. Such a sealing material 17 ′ may be made of a metal material in addition to the same material as the transparent sealing material used in the first example. Examples of the metal material include those made of 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 in the form of a thin film as the sealing material 17 ′, the entire light emitting panel provided with the organic electroluminescent element can be thinned.

  In the case where the organic electroluminescent element EL-2 takes out the emitted light h also from the counter electrode 5-2 side, the material constituting the counter electrode 5-2 is light among the conductive materials described above. A conductive material with good permeability may be selected and used. In this case, a transparent sealing material having light transmittance is used as the sealing material 17 ′.

<Effect of organic electroluminescent element EL-2>
In the organic electroluminescent element EL-2 described above, the electrode layer 1b of the transparent electrode 1 having both conductivity and light transmittance according to the present invention is used as an anode, and a light emitting functional layer 3 and a counter electrode serving as a cathode are formed thereon. 5-2. Therefore, as in the first example, a sufficient voltage is applied between the transparent electrode 1 and the counter electrode 5-2 to realize high-luminance light emission in the organic electroluminescent element EL-2, while the transparent electrode 1 It is possible to increase the luminance by improving the extraction efficiency of the emitted light h from the side. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance.

≪5. Third example of organic electroluminescence device (double-sided light emission type) >>
<Configuration of organic electroluminescent element>
FIG. 5 is a cross-sectional configuration diagram showing a third example of an organic electroluminescent element using the above-described transparent electrode as an example of the electronic device of the present invention. The organic electroluminescent element EL-3 of the third example shown in this figure is different from the organic electroluminescent element EL-1 of the first example described with reference to FIG. 3 in that the transparent electrode 1 is also formed on the transparent substrate 13 ′ side. The light emitting functional layer 3 is sandwiched between the two transparent electrodes 1. Hereinafter, a detailed description of the same components as those in the first example will be omitted, and a characteristic configuration of the organic electroluminescence element EL-3 in the third example will be described.

  The organic electroluminescent element EL-3 shown in FIG. 5 is provided on the transparent substrate 13 ′, and in order from the transparent substrate 13 ′ side, the transparent electrode 1 having the electrode layer 1b serving as an anode, the light emitting functional layer 3, and A transparent electrode 1 having an electrode layer 1b serving as a cathode is laminated in this order. Of these, the two transparent electrodes 1 are characterized in that the transparent electrode 1 of the present invention described above is used. Accordingly, the organic electroluminescent element EL-3 is configured as a double-sided light emitting type in which the emitted light h is extracted from both the transparent substrate 13 'side and the transparent sealing material 17 side opposite to the transparent substrate 13' side.

  The overall layer structure of the organic electroluminescent element EL-3 is not limited, but may be a general layer structure, as in the first example. As an example of the case of the third example, a configuration in which a hole injection layer 3a / a hole transport layer 3b / a light emitting layer 3c / an electron transport layer 3d are provided in this order on the transparent electrode 1 serving as an anode is illustrated. A configuration in which the transparent electrode 1 serving as a cathode is laminated on the upper portion is exemplified. In the illustrated example, the electron transport layer 3d also serves as the electron injection layer and also serves as the nitrogen-containing layer 1a of the transparent electrode 1.

  As described in the first example, the light emitting functional layer 3 may employ various configurations as necessary, and may be provided with a hole blocking layer or an electron blocking layer that is not shown here. . In the above configuration, only the portion sandwiched between the two transparent electrodes 1 becomes the light emitting region in the organic electroluminescent element EL-3, as in the first example.

  Further, in the organic electroluminescent element EL-3 of the present embodiment, the transparent electrode 1 provided on the transparent substrate 13 ′ side is provided in the order of the nitrogen-containing layer 1a and the electrode layer 1b from the transparent substrate 13 ′ side. The light emitting functional layer 3 is directly provided on the electrode layer 1b functioning as an anode. Therefore, the nitrogen-containing layer 1a of the electrode layer 1b may be configured using a material that satisfies the above-described formula (1) or (2), and it is not necessary to use a material having an electron transporting property or an electron injecting property. . In the third embodiment, the transparent electrode 1 provided on the transparent substrate 13 ′ side has been described as a laminated structure of the nitrogen-containing layer 1a and the electrode layer 1b. However, the transparent electrode 1 is a single layer only of the electrode layer 1b. It may be a structure.

  On the other hand, the transparent electrode 1 provided on the light emitting functional layer 3 is provided in order of the nitrogen-containing layer 1a and the electrode layer 1b from the light emitting functional layer 3 side, and emits light with the electrode layer 1b substantially functioning as a cathode. The nitrogen-containing layer 1a is disposed between the functional layer 3 and the functional layer 3. For this reason, the nitrogen-containing layer 1a also serves as a layer constituting a part of the light emitting functional layer 3. Such a nitrogen-containing layer 1a is preferably configured using a material having an electron transporting property or an electron injecting property among materials satisfying the above-described formula (1) or formula (2). Therefore, for example, a material satisfying the formula (1) or the formula (2) is selected from the electron transport materials represented by the general formulas (6) and (7) and the general formula (1) exemplified as the electron transport material. To be used. In this case, since the nitrogen-containing layer 1a provided on the light emitting functional layer 3 is regarded as the light emitting functional layer 3, it can be said that the transparent electrode 1 on the light emitting functional layer 3 has a single-layer structure including only the electrode layer 1b. .

  In the layer configuration as described above, the auxiliary electrode 15 may be provided in contact with the electrode layer 1b of the two transparent electrodes 1 for the purpose of reducing the resistance of the transparent electrode 1. The same as in the example.

  Furthermore, since this organic electroluminescent element EL-3 is a double-sided light emitting type, it is sealed with a transparent sealing material 17 having light transmittance.

<Effect of organic electroluminescent element EL-3>
The organic electroluminescent element EL-3 described above has a configuration in which the transparent electrode 1 having both conductivity and light transmittance of the present invention is used as an anode and a cathode, and the light emitting functional layer 3 is sandwiched therebetween. For this reason, as in the first example, a sufficient voltage is applied between the two transparent electrodes 1 to realize high-intensity light emission in the organic electroluminescent element EL-3, and light emission from the two transparent electrodes 1 side. It is possible to increase the brightness by improving the extraction efficiency of the light h. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance.

≪6. Fourth example of organic electroluminescence device (reverse stacking configuration) >>
<Configuration of organic electroluminescent element>
FIG. 6 is a cross-sectional configuration diagram showing a fourth example of an organic electroluminescent element using the above-described transparent electrode as an example of the electronic device of the present invention. The organic electroluminescent element EL-4 of the fourth example shown in this figure is different from the organic electroluminescent element EL-1 of the first example described with reference to FIG. The electrode 1), the light emitting functional layer 3, and the anode (counter electrode 5-4) are provided and the stacking order is reversed. Hereinafter, the detailed description of the same components as those in the first example will be omitted, and the characteristic configuration of the organic electroluminescence element EL-4 in the fourth example will be described.

  The organic electroluminescent element EL-4 shown in FIG. 6 is provided on the transparent substrate 13 ′, and in order from the transparent substrate 13 ′ side, the transparent electrode 1 having the electrode layer 1b serving as a cathode, the light emitting functional layer 3, and A counter electrode 5-4 serving as an anode is laminated in this order. Of these, the transparent electrode 1 is characterized in that the transparent electrode 1 of the present invention described above is used. For this reason, the organic electroluminescent element EL-4 is configured as a bottom emission type in which the emitted light h is extracted from at least the transparent substrate 13 ′ side.

  The overall layer structure of such an organic electroluminescent element EL-4 is not limited, but may be a general layer structure, as in the first example. As an example of the case of the fourth example, an electron injection layer 3e / electron transport layer 3d / light emitting layer 3c / hole transport layer 3b / hole injection layer 3a are provided in this order on the electrode layer 1b serving as a cathode. A configuration in which a counter electrode 5-4 serving as an anode is laminated on the upper portion is illustrated.

  As described in the first example, the light emitting functional layer 3 may employ various configurations as necessary, and may be provided with a hole blocking layer or an electron blocking layer that is not shown here. . In the configuration as described above, only the portion sandwiched between the transparent electrode 1 and the counter electrode 5-4 becomes a light emitting region in the organic electroluminescent element EL-4, as in the first example.

  Further, in the organic electroluminescent element EL-4 of the present embodiment, the transparent electrode 1 provided on the transparent substrate 13 ′ side is provided with the light emitting functional layer 3 directly on the electrode layer 1b substantially functioning as a cathode. It will be in the state. Therefore, the nitrogen-containing layer 1a of the electrode layer 1b may be configured using a material that satisfies the above-described formula (1) or formula (2), and it is necessary to use a material having a hole transporting property or a hole injecting property. There is no. In the fourth embodiment, the transparent electrode 1 provided on the transparent substrate 13 ′ side has been described as a laminated structure of the nitrogen-containing layer 1a and the electrode layer 1b. However, the transparent electrode 1 is a single layer only of the electrode layer 1b. It may be a structure.

  In the layer configuration as described above, the auxiliary electrode 15 may be provided in contact with the electrode layer 1b of the transparent electrode 1 for the purpose of reducing the resistance of the transparent electrode 1. It is the same.

  Further, the counter electrode 5-4 provided as the anode above the light emitting functional layer 3 is made of the same metal, alloy, organic or inorganic conductive compound as the anode of the first example, and a mixture thereof.

  As a modification of the present embodiment, a configuration in which the anode on the light emitting functional layer 3 is also the transparent electrode 1 is exemplified. In this case, the electrode layer 1b provided on the light emitting functional layer 3 via the nitrogen-containing layer 1a is a substantial anode. The nitrogen-containing layer 1 a provided on the light emitting functional layer 3 also serves as a part of the light emitting functional layer 3. Such a nitrogen-containing layer 1a is preferably configured using a material having a hole transporting property or a hole injecting property among materials satisfying the above-described formula (1) or formula (2). In this case, since the nitrogen-containing layer 1a provided on the light emitting functional layer 3 is regarded as the light emitting functional layer 3, it can be said that the transparent electrode 1 on the light emitting functional layer 3 has a single-layer structure including only the electrode layer 1b.

<Effect of organic electroluminescent element EL-4>
The organic electroluminescent element EL-4 described above uses the transparent electrode 1 having both conductivity and light transmittance according to the present invention as a cathode, and a light emitting functional layer 3 and a counter electrode 5-4 serving as an anode on the upper side. Are provided in this order. Therefore, as in the first example, a sufficient voltage is applied between the transparent electrode 1 and the counter electrode 5-4 to realize high luminance light emission in the organic electroluminescent element EL-4, while the transparent electrode 1 It is possible to increase the luminance by improving the extraction efficiency of the emitted light h from the side. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance.

≪7. Applications of organic electroluminescent devices >>
Since the organic electroluminescent elements having the above-described configurations are surface light emitters as described above, they 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.

  Further, the organic electroluminescent device of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a type for directly viewing a still image or a moving image. It may be used as a 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 joined together in a plane, in accordance with the recent increase in the size of lighting devices and displays.

  The driving 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 electroluminescent elements of the present invention having different emission colors.

  Hereinafter, a lighting device will be described as an example of the application, and then a lighting device in which the light emitting surface is enlarged by tiling will be described.

≪8. Lighting device-1 >>
The illuminating device of this invention has the said organic electroluminescent element.

  The organic electroluminescent element used in the lighting device of the present invention may be designed such that each organic electroluminescent element having the above-described configuration 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.

  In addition, the material used for the organic electroluminescent element of this invention is applicable to the organic electroluminescent element (it is also called white organic electroluminescent element) which produces substantially white light emission. 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. The combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of red, green and blue, or two using the complementary colors such as blue and yellow, blue green and orange. The thing containing the light emission maximum wavelength may be used.

  In addition, the combination of luminescent materials for obtaining multiple luminescent colors is a combination of multiple phosphorescent or fluorescent materials that emit light, fluorescent materials or phosphorescent materials, and light from the luminescent materials. Any combination with a dye material that emits light as light may be used, but in a white organic electroluminescent element, a combination of a plurality of light-emitting dopants may be used.

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

  Further, the light emitting material used for the light emitting layer of such a white organic electroluminescent element is not particularly limited. For example, a backlight in a liquid crystal display element is adapted to a wavelength range corresponding to the CF (color filter) characteristics. In addition, any metal complex according to the present invention or a known light emitting material may be selected and combined to be whitened.

  If the white organic electroluminescent element demonstrated above is used, it is possible to produce the illuminating device which produces substantially white light emission.

≪9. Lighting device-2 >>
FIG. 7 shows a cross-sectional configuration diagram of a lighting device in which a plurality of organic electroluminescent elements having the above-described configurations are used to increase the light emitting surface. In the illuminating device shown in this figure, for example, a plurality of light emitting panels 21 each provided with the above-described organic electroluminescent element EL-2 of the second example are arranged on a support substrate 23 on a transparent substrate 13 ′ (ie, a tie type). The light emitting surface is increased in area by ringing). The support substrate 23 may also serve as the sealing material 17 ′. Each of the support substrates 23 and the transparent substrate 13 ′ of the light-emitting panel 21 holds the organic electroluminescent element EL-2 in a sandwiched state. The light emitting panel 21 is tiled. An adhesive 19 may be filled between the support substrate 23 and the transparent substrate 13 ′, thereby sealing the organic electroluminescent element EL-2. In addition, the edge part of the electrode layer 1b of the transparent electrode 1 which is an anode, and the counter electrode 5-2 which is a cathode are exposed around the light emission panel 21. FIG. However, only the exposed portion of the counter electrode 5-2 is shown in the drawing.

  In the lighting device having such a configuration, the center of each light emitting panel 21 is a light emitting area A, and a non-light emitting area B is generated between the light emitting panels 21. For this reason, a light extraction member for increasing the light extraction amount from the non-light emitting region B may be provided in the non-light emitting region B of the light extraction surface 13a. As the light extraction member, a light collecting sheet or a light diffusion sheet can be used.

  In addition, although the light emitting panel 21 tiling on the support substrate 23 is exemplified by the one provided with the organic electroluminescent element EL-2, the above-described organic electroluminescent elements are used for the light emitting panel 21. In the case where the support substrate 23 is on the light extraction side, the light-transmitting support substrate 23 may be used.

<< Preparation of transparent electrode-1 >>
As described below, each of the transparent electrodes of Samples 1-1 to 1-12 was fabricated such that the area of the conductive region was 5 cm × 5 cm.

  In Sample 1-1, a transparent electrode having a single layer structure composed of an electrode layer using silver was produced. In Samples 1-2 to 1-12, as shown in Table 1 below, transparent electrodes having a laminated structure of a nitrogen-containing layer composed of each compound and an electrode layer using silver on the upper part were prepared.

  In the production of the transparent electrode of Sample 1-2, anthracene containing no nitrogen was used as the compound constituting the nitrogen-containing layer. In the production of the transparent electrode of Sample 1-3, the following spiro-DPVBi containing no nitrogen was used as a compound constituting the nitrogen-containing layer.

  Moreover, in preparation of each transparent electrode of sample 1-4-1-12, as a compound which comprises a nitrogen-containing layer, the following TPD (diamine derivative), a porphyrin derivative, and the material which comprises a nitrogen-containing layer previously Compound 99, 94, 10 shown as No. 11 and Compound No. 11 were used. These compounds are compounds containing nitrogen.

  Of these compounds, compound 10 is a compound included in general formula (1). Compound No. 11 is a compound included in the general formula (2) and is also used in Example 2 below.

<Procedure for producing transparent electrode of Sample 1-1>
First, a transparent alkali-free glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus and attached to a vacuum tank of the vacuum 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 tank to 4 × 10 ⁻⁴ Pa, the resistance heating boat was energized and heated, and the deposition rate was 0.1 nm / second to 0.2 nm / second, and a single layer made of silver having a thickness of 8 nm. A transparent electrode having a layer structure was formed.

<Procedure for producing transparent electrodes of Samples 1-2 to 1-14>
A transparent non-alkali glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus. Moreover, in preparation of each transparent electrode, the said anthracene, TPD, and each other compound were put into the resistance heating boat made from a tantalum, respectively. These substrate holder and heating boat were attached to the first vacuum chamber of the vacuum deposition apparatus. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber.

In this state, first, the first vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then heated by energizing a heating boat containing each compound, at a deposition rate of 0.1 nm / second to 0.2 nm / second. A nitrogen-containing layer composed of each compound having a film thickness of 25 nm was provided on the substrate.

Next, the base material formed up to the nitrogen-containing layer is transferred to the second vacuum chamber while maintaining a vacuum, and after the pressure in the second vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing silver is energized and heated. did. Thus, an electrode layer made of silver with each film thickness (3 nm to 15 nm) is formed at a deposition rate of 0.1 nm / second to 0.2 nm / second, and has a laminated structure of the nitrogen-containing layer and the upper electrode layer. Each transparent electrode of Sample 1-2 to 1-14 was obtained. Table 1 shows the film thicknesses of the electrode layers in Samples 1-1 to 1-14.

<Measurement of coverage in each sample of Example 1>
Scanning electron microscope images were taken on the surfaces of the electrode layers of Samples 1-1 to 1-14 produced as described above, and the coverage was obtained by image processing. FIG. 8A shows a secondary electron image (SEM image) of the electrode layer produced as Sample 1-1 by a scanning electron microscope. FIG. 8B shows a processed image obtained by binarizing the contrast of the SEM image by image processing. The black display portion in FIG. 8B corresponds to the opening a, and the white display portion corresponds to the coating surface with the conductive material. Similarly, FIGS. 9 to 11 show secondary electron images and processed images of Sample 1-4, Sample 1-11, and Sample 1-12, respectively. Table 1 shows the coverage obtained thereby.

<Evaluation-1 of each sample of Example 1>
The light transmittance was measured for each transparent electrode of Samples 1-1 to 1-14 produced above. The light transmittance was measured using a spectrophotometer (U-3300, manufactured by Hitachi, Ltd.), using the same substrate as the sample as the baseline. The results are shown in Table 1 above.

<Evaluation-2 of each sample of Example 1>
The sheet resistance value was measured about each transparent electrode of the samples 1-1 to 1-14 produced above. The sheet resistance value was measured using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Corporation) by a 4-terminal 4-probe method constant current application method. The results are shown in Table 1 above.

<Evaluation result of Example 1>
As is apparent from Table 1, the transparent electrodes of Samples 1-4 to 1-13, that is, having a film thickness of 12 nm or less capable of measuring sheet resistance, and having a coverage of 70% or more and 100% or less, silver The transparent electrode according to the present invention having the electrode layer composed of the above has a light transmittance of 50% or more. On the other hand, the transparent electrodes of Samples 1-1 to 1-3, that is, transparent electrodes outside the scope of the present invention with a coverage of 70% or less, not only cannot measure sheet resistance, but also have light transmittance. It was as low as 42% or less. Further, the transparent electrode of Sample 1-14, that is, the transparent electrode having an electrode layer with a film thickness of 15 nm or more, had a low light transmittance of 37%, although the sheet resistance was measurable.

  Thereby, it was confirmed that the transparent electrode of this invention structure has a high light transmittance and electroconductivity.

  In addition, when Samples 1-4 to 1-8 and Sample 1-11 having an electrode layer thickness of 8 nm were compared, it was confirmed that the larger the coverage, the lower the sheet resistance and the higher the light transmittance. . Furthermore, when comparing the sheet resistance of Samples 1-9 to 1-14 with the same nitrogen-containing layer material (compound 10) and different electrode layer thicknesses, the larger the electrode layer thickness and the higher the coverage, the more the sheet It was confirmed that the resistance was low.

  On the other hand, when the light transmittances of the similar samples 1-9 to 1-14 are compared, the light transmittance shows a maximum value when the film thickness of the electrode layer is about 5 nm to 8 nm. Then, the light transmittance was lowered. Thereby, it was confirmed that the optimal film thickness of the electrode layer using silver is in the range of 5 nm to 8 nm.

<< Preparation of transparent electrode-2 >>
As described below, each of the transparent electrodes of Samples 2-1 to 2-12 was fabricated such that the area of the conductive region was 5 cm × 5 cm.

  In Sample 2-1, a transparent electrode having a single layer structure composed of an electrode layer made of silver and having a thickness of 5 nm was prepared. In Samples 2-2 to 2-12, a transparent electrode having a laminated structure of a nitrogen-containing layer composed of each compound and an electrode layer having a film thickness of 5 nm using silver on the top was prepared.

  In the production of the transparent electrode of Sample 2-2, anthracene (compound No. 01) containing no nitrogen was used as the compound constituting the nitrogen-containing layer.

  On the other hand, in the production of the transparent electrodes of Samples 2-3 to 2-12, the compounds No. 02 to No. 11 containing nitrogen as shown below were used as the compounds constituting the nitrogen-containing layer. .

  Among these compounds, compounds No. 03 and No. 08 are compounds included in the general formula (1), and compound No. 11 is a compound included in the general formula (2). Compound No. 4 is Compound 31 previously shown as the material constituting the nitrogen-containing layer. Compound No. 5 is the compound 34 previously shown as the material constituting the nitrogen-containing layer. Compound No. 6 is the compound 33 previously shown as the material constituting the nitrogen-containing layer. Further, Compound No. 8 is Compound 10 previously shown as a material constituting the nitrogen-containing layer.

  Table 2 below shows the number of nitrogen atoms [n] in the compound that stably binds to silver (Ag) for each of the compounds No. 02 to No. 11 used in Samples 2-3 to 2-12. The interaction energy [ΔE] between silver (Ag) and nitrogen (N) in the compound, the surface area [s] of the compound, and the effective action energy [ΔEef] calculated from these were shown. The dihedral angle [D] and [ΔE] formed by the nitrogen atom and silver with respect to the ring containing the nitrogen atom in the compound for obtaining [n] are Gaussian 03 (Gaussian, Inc., Wallingford, CT , 2003). In each of compounds No. 02 to No. 11 used in Samples 2-3 to 2-12, nitrogen atoms having a dihedral angle D <10 degrees were counted in a number [n].

  In Compound No. 02, the effective action energy [ΔEef] indicating the relationship between the nitrogen atom (N) contained in the compound and silver (Ag) constituting the electrode layer is ΔEef> −0.1. On the other hand, the effective action energy [ΔEef] of the compounds No. 03 to No. 11 is ΔEef ≦ −0.1.

<Procedure for producing transparent electrode of sample 2-1>
First, a transparent alkali-free glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus and attached to a vacuum tank of the vacuum 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 tank to 4 × 10 ⁻⁴ Pa, the resistance heating boat was energized and heated, and the deposition rate was 0.1 nm / second to 0.2 nm / second, and a single layer made of silver having a film thickness of 5 nm. A transparent electrode having a layer structure was formed.

<Procedure for producing transparent electrodes of Samples 2-2 to 2-12>
A transparent non-alkali glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus. Moreover, in preparation of each transparent electrode, each said compound No.01-No.11 was put into the resistance heating boat made from a tantalum. These substrate holder and heating boat were attached to the first vacuum chamber of the vacuum deposition apparatus. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber.

In this state, first, the first vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then heated by energizing a heating boat containing each compound, at a deposition rate of 0.1 nm / second to 0.2 nm / second. A nitrogen-containing layer composed of each compound having a film thickness of 25 nm was provided on the substrate.

Next, the base material formed up to the nitrogen-containing layer is transferred to the second vacuum chamber while maintaining a vacuum, and after the pressure in the second vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing silver is energized and heated. did. As a result, an electrode layer made of silver having a film thickness of 5 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second, and a sample 2-2 to a laminated structure of a nitrogen-containing layer and the upper electrode layer was formed. 2-12 transparent electrodes were obtained.

<Evaluation of each sample of Example 2>
The sheet resistance value was measured for each transparent electrode of Samples 2-1 to 2-12 produced above. The sheet resistance value was measured using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Corporation) by a 4-terminal 4-probe method constant current application method. The results are shown in Table 2 above.

<Evaluation results of Example 2>
As is clear from Table 2, the transparent electrodes of Samples 2-4 to 2-12, in which the nitrogen-containing layer is formed using the compounds No. 03 to No. 11 in which the effective action energy ΔEef is ΔEef ≦ −0.1, Although the electrode layer using silver that carries substantial conductivity is an ultra-thin film having a thickness of 5 nm, the sheet resistance value can be measured, and a single-layer growth type (FW-type) film It was confirmed that the film was formed with a substantially uniform film thickness by the growth. On the other hand, the transparent electrode of Sample 2-1 having a single layer structure without a nitrogen-containing layer, the transparent electrode of Sample 2-2 having a nitrogen-containing layer formed using Compound No. 1 containing no nitrogen, and It was impossible to measure the sheet resistance of the transparent electrode of Sample 2-3 in which the nitrogen-containing layer was configured using Compound No. 02 where ΔEef> −0.1.

  FIG. 12 shows the relationship between the effective action energy ΔEef for the compounds No. 03 to No. 11 constituting the nitrogen-containing layer and the sheet resistance measured for each transparent electrode. From this FIG. 12, it is clear that the sheet resistance of the transparent electrode tends to decrease as the value of ΔEef decreases in the range where the effective action energy ΔEef is confirmed to be −0.4 ≦ ΔEef ≦ −0.1. Further, when the effective action energy ΔEef is in the range of −0.4 ≦ ΔEef ≦ −0.2, the sheet resistance is 1000 [Ω / sq. It is further preferable that the following is maintained.

  As described above, by selecting and using a compound that constitutes the nitrogen-containing layer using the effective action energy ΔEef as an index, an electrode film (that is, a transparent electrode) that is a thin film but has a low resistance in order to obtain light transmittance can be obtained. It was confirmed.

  A double-sided light emitting organic electroluminescent device using each of the transparent electrodes of Samples 1-1 to 1-14 produced in Example 1 as a cathode was produced. A manufacturing procedure will be described with reference to FIG.

  First, a light transmissive counter electrode 5-1 made of ITO as an anode was formed on the transparent substrate 13 by sputtering. At this time, the transparent substrate 13 is fixed to a substrate holder of a sputtering apparatus to which an ITO target is attached as a counter electrode material. Next, in the processing chamber of the sputtering apparatus, a film was formed at a film formation rate of 0.3 nm / second to 0.5 nm / second, and a light-transmitting counter electrode 5-1 made of ITO having a film thickness of 150 nm was formed as an anode.

  Next, the transparent substrate 13 on which the counter electrode 5-1 is formed is transferred from the sputtering apparatus to a commercially available vacuum deposition apparatus, fixed to the substrate holder of the vacuum deposition apparatus, and deposited on the surface where the counter electrode 5-1 is formed. Masks were placed facing each other. Moreover, each material which comprises the light emission functional layer 3 was filled with the optimal quantity for film-forming of each layer in each heating boat in a vacuum evaporation system. In addition, the heating boat used what was produced with the resistance heating material made from tungsten.

Next, the inside of the vapor deposition chamber of the vacuum vapor deposition apparatus was depressurized to a vacuum degree of 4 × 10 ⁻⁴ Pa, and each layer was formed as follows by sequentially energizing and heating the heating boat containing each material.

  First, as a hole transport injection material, a heating boat containing α-NPD represented by the following structural formula is energized and heated, and the hole transport / hole transport layer that serves as both the hole injection layer and the hole transport layer made of α-NPD The injection layer 31 was formed on the counter electrode 5-1. At this time, the deposition rate was 0.1 nm / second to 0.2 nm / second, and the film thickness was 20 nm.

  Next, the heating boat containing the host material H4 having the structural formula shown above and the heating boat containing the phosphorescent compound Ir-4 having the structural formula shown above were independently energized, A light emitting layer 32 made of H4 and phosphorescent compound Ir-4 was formed on the hole transport / injection layer 31. 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. The film thickness was 30 nm.

  Next, a heating boat containing BAlq represented by the following structural formula as a hole blocking material was energized and heated to form a hole blocking layer 33 made of BAlq on the light emitting layer 32. At this time, the deposition rate was 0.1 nm / second to 0.2 nm / second, and the film thickness was 10 nm.

  Thereafter, a heating boat containing the compound 10 having the structural formula shown above as an electron transporting material and a heating boat containing potassium fluoride are energized independently to transport the electron consisting of the compound 10 and potassium fluoride. A layer 34 was formed on the hole blocking layer 33. At this time, the energization of the heating boat was adjusted so that the deposition rate was compound 10: potassium fluoride = 75: 25. The film thickness was 30 nm.

  Next, a heating boat containing potassium fluoride as an electron injection material was energized and heated, and an electron injection layer 35 made of potassium fluoride was formed on the electron transport layer 34. At this time, the deposition rate was 0.01 nm / second to 0.02 nm / second, and the film thickness was 1 nm.

  Thereafter, a film was formed on the electron injection layer 35 using the transparent electrodes 1 of the samples 1-1 to 1-14 described in Example 1 as cathodes. Thus, the organic electroluminescent element EL was formed on the transparent substrate 13.

  Next, the organic electroluminescent element EL is covered with a sealing material 17 made of a glass substrate having a thickness of 300 μm, and the adhesive 19 (between the sealing material 17 and the transparent substrate 13 is surrounded by the organic electroluminescent element EL. Sealing material) was filled. As the adhesive 19, an epoxy photocurable adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) was used. The adhesive 19 filled between the sealing material 17 and the transparent substrate 13 is irradiated with UV light from the glass substrate (sealing material 17) side, and the adhesive 19 is cured to form the organic electroluminescent element EL. Sealed.

  In the formation of the organic electroluminescent element EL, 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 transparent substrate 13 is defined as the light emitting region A, and the entire light emitting region A is formed. A non-light emitting region B having a width of 0.25 cm was provided on the circumference. Further, the counter electrode 5-1 as the anode and the transparent electrode 1 as the cathode are insulated by the light emitting functional layer 3 from the hole transport / injection layer 31 to the electron injection layer 35, and the periphery of the transparent substrate 13 The terminal part was formed in the shape pulled out.

  As described above, the organic electroluminescent elements EL were provided on the transparent substrate 13, and the light emitting panels of Samples 3-1 to 3-14 in which the organic electroluminescent elements EL were sealed with the sealing material 17 and the adhesive 19 were obtained. In each of these light emitting panels, each color of emitted light h generated in the light emitting layer 32 is extracted from both the transparent electrode 1 side, that is, the transparent substrate 13 side, and the counter electrode 5-1 side, that is, the sealing material 17 side. .

<Evaluation-1 of each sample of Example 3>
The light transmittance was measured for the organic electroluminescent elements EL produced in Samples 3-1 to 3-14. The light transmittance was measured using a spectrophotometer (U-3300, manufactured by Hitachi, Ltd.), using the same substrate as the sample as the baseline. The results are also shown in Table 3 below.

<Evaluation-2 of each sample of Example 3>
The driving voltage was measured for the organic electroluminescent elements EL produced in Samples 3-1 to 3-14. The results are also shown in Table 3 below. In the measurement of the driving voltage, the front luminance on both sides of the transparent electrode 1 side (that is, the transparent substrate 13 side) and the counter electrode 5-1 side (that is, the sealing material 17 side) of each organic electroluminescent element EL is measured. The voltage when the sum is 1000 cd / m ² was measured as the drive voltage. A spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used for measuring the luminance. A smaller value of the obtained drive voltage indicates a more favorable result.

<Evaluation results of Example 3>
As is apparent from Table 3, the organic electroluminescence elements of Samples 3-4 to 3-13 using the transparent electrode 1 of the present invention as the cathode have an element transmittance of 40% or more, and application of drive voltage Emission due to was confirmed. On the other hand, the organic electroluminescent elements using the transparent electrodes that are not in the structure of the present invention of Samples 3-1 to 3-3 and 3-14 as the cathode have an element transmittance of less than 40% or a voltage. Even when applied, no light was emitted.

  As a result, it was confirmed that the organic electroluminescence device using the transparent electrode of the present invention can emit light with high luminance at a low driving voltage. In addition, it was confirmed that the driving voltage for obtaining the predetermined luminance can be reduced and the light emission life can be improved.

  DESCRIPTION OF SYMBOLS 1 ... Transparent electrode, 1b ... Electrode layer, EL, EL-1, EL-2, EL-3, EL-4 ... Organic electroluminescent element (electronic device), a ... Opening

Claims (5)

A transparent electrode having a film thickness of 12 nm or less capable of measuring sheet resistance, a covering ratio of 70% to 100%, and an electrode layer made of silver.   The transparent electrode according to claim 1, wherein the film thickness is 8 nm or less. The transparent electrode according to claim 1, wherein the coverage is 80% or more and 100% or less. An electronic device comprising the transparent electrode according to claim 1. The electronic device according to claim 4, wherein the electronic device is an organic electroluminescent element.