JP4990264B2 - Liquid material - Google Patents

Description

The present invention relates to a liquid material .

Examples of organic semiconductor elements using organic semiconductor materials or organic semiconductor materials and organic-inorganic composite semiconductor materials include organic light-emitting elements, organic transistors, and organic solar cells.
Among these, the organic electroluminescence (EL) element in which the light-emitting organic layer (organic electroluminescence layer) is provided between the cathode and the anode can significantly reduce the applied voltage compared to the inorganic EL element. Various light emitting elements can be manufactured.

Currently, in order to obtain a higher performance organic EL device, a device structure in which various layers are provided between a cathode and a light emitting organic layer (light emitting layer) or between an anode and an organic light emitting layer has been proposed. Active research is being conducted.
One of these layers is an electron transport layer provided between the cathode and the organic light emitting layer, and an electron injection layer provided between the electron transport layer and the cathode. Improving the performance of the injection layer is urgent because it largely depends on the device characteristics.
For example, in Patent Document 1, by co-evaporating an electron transporting organic compound and a metal compound containing an alkali metal that is a metal having a low work function, by mixing the metal compound into the electron injection layer, A configuration for improving the characteristics of the electron injection layer has been proposed.

However, the electron injection layer having such a configuration is only intended to lower the driving voltage and improve the light emission efficiency, and it is difficult to say that the durability has been improved.
In addition, since the electron injection layer is formed by vacuum deposition, a large facility is required, and it is difficult to precisely adjust the deposition rate when two or more materials are deposited at the same time, resulting in poor productivity. There is also.

JP 2005-63910 A

An object of the present invention is to provide a liquid material obtained by dissolving an organic-inorganic composite semiconductor material having a high electron-injecting property and electron-transporting property in a solvent.

これにより、効率および耐久性に優れる有機半導体素子の製造に用いる、生産性に優れる液状材料が得られる。
特に、金属塩は、金属イオンを解離しやすいものであるとともに、このような炭素数の単価アルコールは、金属塩の溶解性が高い。このため、高い効率および耐久性に優れる有機発光素子の製造に用いる液状材料が得られる。
本発明の液状材料では、前記アルカリ金属イオンはＣｓイオンであり、前記アルカリ土類金属イオンはＣａイオンであることが好ましい。 The liquid material according to the present invention includes a compound represented by the following general formula (1) (wherein Ar ¹ , Ar ² and Ar ³ have at least an aromatic ring group):
A metal salt having at least one metal ion of alkali metal ions and alkaline earth metal ions;
A protic polar solvent;
Including
The metal salt is dissociated by dissolving in the protic polar solvent ,
When the number of P═O bonds contained in the compound represented by the general formula (1) is A [number] and the number of the metal ions is B [number], the compound is represented by the general formula (1). B / A, which is the amount ratio of the compound and the metal ion, is 0.2 to 1.5.

Thereby, the liquid material excellent in productivity used for manufacture of the organic-semiconductor element excellent in efficiency and durability is obtained.
In particular, the metal salt is easy to dissociate metal ions, and such a monovalent alcohol having a carbon number has high solubility of the metal salt. For this reason, the liquid material used for manufacture of the organic light emitting element excellent in high efficiency and durability is obtained.
In the liquid material of the present invention, it is preferable that the alkali metal ions are Cs ions and the alkaline earth metal ions are Ca ions .

Hereinafter, the organic-inorganic composite semiconductor material of the present invention, the liquid material containing the organic-inorganic composite semiconductor, organic light emitting device, described the preferred embodiments of the light emission device and an electronic apparatus, further, the manufacturing method of the organic light emitting device description An organic light-emitting element, a light-emitting device, and an electronic device are shown in the accompanying drawings.
FIG. 1 is a view schematically showing a longitudinal section of an embodiment of the organic light emitting device of the present invention. In the following description, for convenience of explanation, the upper side in FIG.
An organic light-emitting device (organic electroluminescence device) 1 shown in FIG. 1 transports holes in order from the anode 3 side between an anode 3 provided on a substrate 2, a cathode 7, and the anode 3 and the cathode 7. The layer 4, the organic light emitting layer 5, and the electron transport layer 6 are laminated, and the whole is sealed with a sealing member 8.

The substrate 2 serves as a support for the organic light emitting device 1. Since the organic light emitting device 1 of the present embodiment is configured to extract light from the substrate 2 side (bottom emission type), each of the substrate 2 and the anode 3 is substantially transparent (colorless transparent, colored transparent, or translucent). It is said that.
Examples of the constituent material of the substrate 2 include resin materials such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate, and polyarylate, quartz glass, and soda glass. Such glass materials can be used, and one or more of these can be used in combination.
Although the average thickness of such a board | substrate 2 is not specifically limited, It is preferable that it is about 0.1-30 mm, and it is more preferable that it is about 0.1-10 mm.
In the case where the organic light emitting device 1 is configured to extract light from the side opposite to the substrate 2 (top emission type), the substrate 2 can be either a transparent substrate or an opaque substrate.

Examples of the opaque substrate include a substrate made of a ceramic material such as alumina, an oxide film (insulating film) formed on the surface of a metal substrate such as stainless steel, and a substrate made of a resin material. It is done.
The anode 3 is an electrode that injects holes into the hole transport layer 4 described later. As a constituent material of the anode 3, it is preferable to use a material having a large work function and excellent conductivity.
Examples of the constituent material of the anode 3 include oxides such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), In ₃ O ₃ , SnO ₂ , Sb-containing SnO ₂ , and Al-containing ZnO, Au, Pt, and Ag. Cu, alloys containing these, and the like can be used, and one or more of these can be used in combination.
The average thickness of the anode 3 is not particularly limited, but is preferably about 10 to 200 nm, and more preferably about 50 to 150 nm.

On the other hand, the cathode 7 is an electrode for injecting electrons into an electron transport layer 6 described later, and is provided on the opposite side of the electron transport layer 6 from the organic light emitting layer 5. As a constituent material of the cathode 7, it is preferable to use a material having a small work function.
Examples of the constituent material of the cathode 7 include Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, Yb, Ag, Cu, Al, Cs, Rb, and alloys containing these. These can be used alone or in combination of two or more thereof (for example, a multi-layer laminate).

In particular, when an alloy is used as the constituent material of the cathode 7, it is preferable to use an alloy containing a stable metal element such as Ag, Al, or Cu, specifically, an alloy such as MgAg, AlLi, or CuLi. By using such an alloy as the constituent material of the cathode 7, the electron injection efficiency and stability of the cathode 7 can be improved.
Although the average thickness of such a cathode 7 is not specifically limited, It is preferable that it is about 100-10000 nm, and it is more preferable that it is about 200-500 nm.

In the case of the top emission type, a material having a small work function or an alloy containing these is set to about 5 to 20 nm to have transparency, and a conductive material having high transparency such as ITO is formed on the upper surface thereof to a thickness of about 100 to 500 nm. It will be formed.
In addition, since the organic light emitting device 1 of the present embodiment is a bottom emission type, the cathode 7 is not particularly required to have light transmittance.

On the anode 3, a hole transport layer 4 is provided. The hole transport layer 4 has a function of transporting holes injected from the anode 3 to the organic light emitting layer 5.
Examples of the constituent material of the hole transport layer 4 include metal or metal-free phthalocyanine compounds such as phthalocyanine, copper phthalocyanine (CuPc), iron phthalocyanine, polyarylamine, fluorene-arylamine copolymer, fluorene-bithiophene. Copolymer, poly (N-vinylcarbazole), polyvinylpyrene, polyvinylanthracene, polythiophene, polyalkylthiophene, polyhexylthiophene, poly (p-phenylenevinylene), polytinylenevinylene, pyreneformaldehyde resin, ethylcarbazole formaldehyde resin or The derivative | guide_body etc. are mentioned, Among these, it can use combining 1 type (s) or 2 or more types.
Moreover, the said compound can also be used as a mixture with another compound. As an example, the polythiophene-containing mixture includes poly (3,4-ethylenedioxythiophene / styrene sulfonic acid) (PEDOT / PSS).

The average thickness of the hole transport layer 4 is not particularly limited, but is preferably about 10 to 150 nm, and more preferably about 50 to 100 nm.
An organic light emitting layer 5 is provided on the hole transport layer 4, that is, on one surface side of the anode 3. The organic light emitting layer 5 is supplied (injected) with electrons from an electron transport layer 6 (described later) and holes from the hole transport layer 4. In the organic light emitting layer 5, holes and electrons are recombined, and excitons (excitons) are generated by the energy released upon the recombination, and energy (fluorescence and phosphorous) is returned when the excitons return to the ground state. Light) is emitted (emitted).

As a constituent material of the organic light emitting layer 5, 1,3,5-tris [(3-phenyl-6-tri-fluoromethyl) quinoxalin-2-yl] benzene (TPQ1), 1,3,5-tris [{ Benzene compounds such as 3- (4-t-butylphenyl) -6-trisfluoromethyl} quinoxalin-2-yl] benzene (TPQ2), tris (8-hydroxyquinolinolate) aluminum (Alq ₃ ), factory Low molecular weight compounds such as s (2-phenylpyridine) iridium (Ir (ppy) ₃ ), oxadiazole polymers, triazole polymers, carbazole polymers, polyfluorene polymers, polypara Examples include polymers such as phenylene vinylene polymers, which can be used alone or in combination. The
The average thickness of the organic light emitting layer 5 is not particularly limited, but is preferably about 10 to 150 nm, and more preferably about 50 to 100 nm.

An electron transport layer 6 is provided on the organic light emitting layer 5. The electron transport layer 6 has a function of transporting electrons injected from the cathode 7 to the organic light emitting layer 5.
In this invention, it has the characteristics in the structure (especially organic-inorganic composite semiconductor material to comprise) of this electron carrying layer 6. FIG. This point (characteristic) will be described in detail later.
Although the average thickness of such an electron carrying layer 6 is not specifically limited, It is preferable that it is about 1-100 nm, and it is more preferable that it is about 10-50 nm.

The sealing member 8 is provided so as to cover the organic light emitting element 1 (the anode 3, the hole transport layer 4, the organic light emitting layer 5, the electron transport layer 6, and the cathode 7). And has a function of blocking moisture. By providing the sealing member 8, effects such as improvement of the reliability of the organic light emitting element 1 and prevention of deterioration / deterioration (improvement of durability) are obtained.
Examples of the constituent material of the sealing member 8 include Al, Au, Cr, Nb, Ta, Ti, alloys containing these, silicon oxide, various resin materials, and the like. In addition, when using the material which has electroconductivity as a constituent material of the sealing member 8, in order to prevent a short circuit, between the sealing member 8 and the organic light emitting element 1, as needed, an insulating film Is preferably provided.
Further, the sealing member 8 may be formed in a flat plate shape so as to face the substrate 2 and be sealed with a sealing material such as a thermosetting resin.

Now, in order to improve the electron transport characteristics of the electron transport layer 6 mainly composed of an organic compound containing a phosphorus atom, and the characteristics and durability of the organic light-emitting device 1 manufactured using the electron transport layer 6. We studied earnestly.
As a result, the following general formula (1)

（式中、Ａｒ^１、Ａｒ^２およびＡｒ^３は、互いに独立して置換基を有してもよい芳香族環基を示す。）
で表される化合物を主材料とする電子輸送層６中に、アルカリ金属、アルカリ土類金属または希土類金属を金属イオンとして混入することにより、有機発光素子１の発光特性（発光輝度の上昇、駆動電圧の低下、発光効率の向上等）および耐久性の向上を図り得ることを見出した。

(In the formula, Ar ¹ , Ar ² and Ar ³ each independently represent an aromatic ring group which may have a substituent.)
By mixing alkali metal, alkaline earth metal or rare earth metal as a metal ion in the electron transport layer 6 containing a compound represented by the following formula as a main material, the light emission characteristics of the organic light emitting device 1 (increased emission luminance, driving) It has been found that the voltage can be lowered, the luminous efficiency can be improved, and the durability can be improved.

It is assumed that the increase in light emission luminance and the decrease in drive voltage are caused by the following factors. That is, first, when the cathode 7 is formed on the electron transport layer 6 by a vacuum deposition method or the like, the metal ions existing in the vicinity of the interface between the electron transport layer 6 and the cathode 7 have a low work function. By being reduced to the metal state, the efficiency of electron injection from the cathode 7 to the electron transport layer 6 is improved, and secondly, the phosphorus atom contained in the compound represented by the general formula (1) Between the energy levels of organic compounds due to chemical interactions (for example, ionic bonds, coordination bonds, etc.), that is, HOMO (highest occupied molecular orbital) and LUMO ( The lowest unoccupied molecular orbital) changes to a relatively low level. For these reasons, the electron injection barrier at the interface between the electron transport layer 6 and the cathode 7 is reduced, the electron injection efficiency from the cathode 7 to the electron transport layer 6 is improved, and the electron injection into the organic light emitting layer 5 is further improved. To be effective. As a result, it is considered that the emission luminance increases and the drive voltage decreases.
Further, as described above, the improvement of the light emission efficiency suppresses that holes that have not been recombined are sent to the cathode 7 due to the decrease in the HOMO level, and the holes become the organic light emitting layer 5 of the electron transport layer 6. As a result of the effective accumulation at the interface, it can be inferred that there is a large factor in that the accumulated holes can again contribute to recombination.

On the other hand, the improvement in durability is caused by the occurrence of chemical interaction between the compound represented by the general formula (1) and the metal ion, whereby the diffusion of the metal ion to the organic light emitting layer 5 is suppressed, and the metal ion In addition, the stabilization of the structure of the organic compound by the chemical interaction suppresses changes such as distortion of the three-dimensional structure during electron transport (delivery). It is inferred that there is a major factor in stabilizing the layer 6.
The present invention has been made based on such knowledge, and the electron transport layer 6 is represented by the following general formula (1).

（式中、Ａｒ^１、Ａｒ^２およびＡｒ^３は、互いに独立して置換基を有してもよい芳香族環基を示す。）
で表される化合物と、アルカリ金属イオン、アルカリ土類金属イオンおよび希土類金属イオンのうちの少なくとも１種の金属イオンとを含む材料を主材料として構成したことに特徴を有する。

(In the formula, Ar ¹ , Ar ² and Ar ³ each independently represent an aromatic ring group which may have a substituent.)
And a material containing at least one metal ion selected from the group consisting of alkali metal ions, alkaline earth metal ions and rare earth metal ions.

Since the compound represented by the general formula (1) has a phosphorus atom, it has a moderately high electronegativity, and in the structure of the compound represented by the general formula (1), some electrons are present on the atom side. Can be biased. For this reason, the chemical interaction between the compound represented by the general formula (1) and the metal ion can be further enhanced. As a result, the structure of the compound represented by the general formula (1) is further stabilized, The diffusion of metal ions can be suppressed. Moreover, since the said atom has a moderately high bond order, it has an unpaired electron which interacts with a metal ion, and forms a bond easily with another element.
Here, in the general formula (1), Ar ¹ , Ar ² and Ar ³ each independently represent an aromatic ring group which may have a substituent.

Although carbon number of an aromatic ring group is not specifically limited, It is preferable that it is 2-20, and it is more preferable that it is 2-15.
Specifically, monocyclic aromatic hydrocarbon groups such as benzene ring (phenyl group), monocyclic rings such as thiophene ring, triazine ring, furan ring, pyrazine ring, pyridine ring, thiazole ring, imidazole ring, pyrimidine ring Condensed polycyclic aromatic hydrocarbon group such as heterocyclic group, naphthalene ring and anthracene ring, condensed polycyclic heterocyclic group such as thieno [3,2-b] furan ring, biphenyl ring, terphenyl Ring assembled aromatic hydrocarbon groups such as rings, ring assembled heterocyclic groups such as bithiophene rings and bifuran rings, acridine rings, isoquinoline rings, indole rings, carbazole rings, carboline rings, quinoline rings, dibenzofuran rings, cinnolines Aromatic rings such as rings, thionaphthene rings, 1,10-phenanthroline rings, phenothiazine rings, purine rings, benzofuran rings, silole rings, and heterocycles Those which consist of a combination of thereof. Among these, a benzene ring (phenyl group) is particularly preferable. Thereby, the structure of the compound represented by the general formula (1) can be further stabilized, and the organic light-emitting device 1 excellent in light emission efficiency, durability, and lifetime, and excellent in electron injection property and electron transport property is obtained. Can be provided.
Examples of the substituent that can be bonded to the aromatic ring group include an alkyl group, a halogen atom, a cyano group, a nitro group, an amino group, an aryl group, a diarylphosphinyl group, an alkoxy group, and the following general formula (2).

（式中、Ａｒ^４およびＡｒ^５は、互いに独立して置換基を有してもよい芳香族環基を示す。）
で表される基などが挙げられる。

(In the formula, Ar ⁴ and Ar ⁵ each independently represent an aromatic ring group which may have a substituent.)
Group represented by these.

Of these substituents, the compound represented by the general formula (2) is preferable. Thereby, the organic light emitting element 1 excellent in luminous efficiency, durability, and lifetime, and excellent in electron injection property and electron transport property can be provided.
Although carbon number of an alkyl group is not specifically limited, It is preferable that it is 1-20, and it is more preferable that it is 1-10. Specific examples include a methyl group, an ethyl group, a butyl group, and a hexyl group. Also, a substituted or unsubstituted aromatic ring can be formed together with the carbon atom of the benzene ring to which the substituent is bonded. Thereby, the structure of the compound represented by the general formula (1) can be further stabilized. In addition, examples of the substituent when the aromatic ring is substituted include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, an amino group, an aryl group, and a diarylphosphinyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the aryl group include aromatic hydrocarbon groups such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a terphenyl group, and a pyrenyl group, which may be unsubstituted or substituted. In addition, examples of the substituent when substituted include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, an amino group, an aryl group, and a diarylphosphinyl group.
The aryl of the diarylphosphinyl group is the same as the aryl group.

Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is 1-20, and it is more preferable that it is 1-10. Specific examples include a methoxy group, an ethoxy group, a butoxy group, and a pentoxy group. Thereby, the structure of the compound represented by the general formula (1) can be further stabilized.
The aromatic ring group of Ar ⁴ and Ar ^{5 in} the general formula (2) and the substituent that can be substituted with the aromatic ring group are the same as those described for Ar ¹ , Ar ² and Ar ³ , A phenyl group is preferred. Thereby, the structure of the compound represented by the general formula (1) can be further stabilized, and the organic light-emitting device 1 excellent in light emission efficiency, durability, and lifetime, and excellent in electron injection property and electron transport property is obtained. Can be provided.
Specific examples of the compound represented by the general formula (1) are described below by combining the Ar ^{1 to} Ar ³ aromatic ring groups of the compound represented by the general formula (1) described above and substituents that can be substituted therefor. Show. The following specific examples are merely representative and are not particularly limited to these.
(I): Compound having one substituent represented by the general formula (2)

(II): Compound having two substituents represented by the general formula (2)

(III): Compound having three substituents represented by the general formula (2)

The content of the compound represented by the general formula (1) is preferably 30 to 70 wt% with respect to the constituent material of the electron transport layer 6.
In addition, the compound represented by General formula (1) is compoundable by a well-known method, for example, the method described in WO2005 / 104628.
On the other hand, as the metal ion, depending on the type of the compound represented by the general formula (1), alkali metal ions such as Li, Na and K, alkaline earth metal ions such as Mg, Ca and Sr, or Yb and Sc. , Y, and other rare earth metal ions are appropriately selected. As the compound represented by the general formula (1), for example, when a compound represented by the chemical formula 11 (particularly chemical formula 12) is used, metal ions such as Li, Cs, Ca, Mg, and Yb are preferable. is there. These metal ions may be used in combination of two or more.

  The electron transport layer 6 is mainly composed of a material containing a compound represented by the general formula (1) and at least one metal ion of alkali metal ions, alkaline earth metal ions, and rare earth metal ions. Preferably, the material is more preferably 31 to 100 wt%, and most preferably 50 to 100 wt% with respect to the constituent material of the electron transport layer 6. Thereby, the electron injection property and the electron transport property are improved, and the organic light emitting device 1 having excellent light emission efficiency and durability can be obtained.

In the electron transport layer 6, the amount ratio of the compound represented by the general formula (1) and the metal ion is such that the number of P═O bonds contained in the compound represented by the general formula (1) is represented by A [ And B / A is preferably 0.05 or more, more preferably 0.2 or more, and about 0.2 to 1.5. Most preferably. By setting B / A in the above range, metal ions can be present in excess and deficiency with respect to the compound represented by the general formula (1), and the structure of the compound represented by the general formula (1) can be further increased. It can be reliably stabilized. Further, the efficiency of injecting electrons from the cathode 7 to the electron transport layer 6 by the action of metal ions can be sufficiently improved. For this reason, the characteristics of the electron transport layer 6 can be further improved. Furthermore, in the electron transport layer 6, the number of metal ions that do not cause a chemical interaction with the compound represented by the general formula (1) can be sufficiently reduced, and the metal ions diffuse into the organic light emitting layer 5. Can be surely prevented. As a result, it is possible to suitably prevent the luminance of light emitted from the organic light-emitting element 1 from decreasing with time and driving.
A material containing the compound represented by the general formula (1) constituting the electron transport layer 6 and at least one metal ion of alkali metal ions, alkaline earth metal ions, and rare earth metal ions, It can also be used as an organic-inorganic composite semiconductor material.

Ar ¹ , Ar ² and Ar ^{3 of the} compound represented by the general formula (1), Ar ⁴ and Ar ^{5 of the} compound represented by the general formula (2), respective substituents, preferred embodiments, alkali metal ions, alkaline earth The content of such metal ions and rare earth metal ions and such materials are the same as those described for the electron transport layer 6.
Further, in the organic-inorganic composite material, the quantitative ratio of the compound represented by the general formula (1) and the metal ion is the number of P═O bonds contained in the compound represented by the general formula (1). The value of B / A when the number is [number] and the number of metal ions is B [number] is the same as that described for the electron transport layer 6.
Such a material has high electron injecting property and electron transporting property, and is excellent in durability and life, so that it can be used as a semiconductor material for various devices.

In addition, these organic-inorganic composite materials can be used as various liquid materials by including a solvent.
As such a solvent, a solvent that does not easily swell or dissolve the organic light emitting layer 5 when used in the organic light emitting device 1 is preferable. Thereby, it is possible to prevent the light emitting material from being altered or deteriorated, or the organic light emitting layer 5 from being dissolved and the film thickness from being extremely reduced. As a result, it is possible to prevent a decrease in the light emission efficiency of the organic light emitting device 1.

Moreover, what melt | dissolves a metal compound easily and dissociates a metal ion is preferable. Specifically, it is preferable to use a protic polar solvent.
Examples of the protic polar solvent include water, methanol, ethanol, propanol, butanol, benzyl alcohol, monovalent alcohols such as diethylene glycol monomethyl ether, alcohols such as polyhydric alcohols such as ethylene glycol and glycerin, acetic acid, formic acid, ( Carboxylic acids such as (meth) acrylic acid, amines such as ethylenediamine and diethylamine, formamide, amides such as N, N-dimethylformamide, phenols, phenols such as p-butylphenol, acetylacetone, diethyl malonate Such active methylene compounds and the like can be mentioned, and one or more of these can be used in combination.

Especially, what has at least 1 sort (s) of water and alcohol as a main component is preferable. Since water and alcohols have high solubility of metal compounds, the use of a protic polar solvent that contains at least one of water and alcohols as a main component ensures that metal ions are extracted from the metal compounds. The liquid material can be easily prepared.
In particular, the alcohol is preferably a monohydric alcohol having 1 to 7 carbon atoms, preferably 1 to 4 carbon atoms. Such a monohydric alcohol having a carbon number is preferable in that the solubility of the metal compound is high. For example, when dissolved cesium carbonate as a metal compound _(Cs 2 CO ₃₎ in the unit price alcohol (R-OH), by the following reactions, Cs ions (metal ions) are believed to dissociate.

Cs ₂ CO ₃ + 2ROH → 2Cs (OR) + CO ₂ + H ₂ O
Cs (OR) + H ₂ O → Cs ⁺ + OH ⁻ + ROH
In addition, in the liquid material containing the organic-inorganic composite semiconductor material, the compound represented by the general formula (1) and the metal compound are converted into the compound represented by the general formula (1) in the obtained electron transport layer 6. The number A [number] of P = O bonds contained and the number B [number] of metal ions are mixed so as to have the same relationship as described in the organic-inorganic composite semiconductor material.

The metal compound having at least one metal ion among alkali metal ions, alkaline earth metal ions, and rare earth metal ions is preferably a metal salt, a metal complex, and a metal alkoxide. Thereby, the liquid material which is easy to dissociate a metal ion, and is used for manufacture of the organic-semiconductor element which is excellent in high efficiency and durability, and is further excellent in productivity is obtained. You may use these in combination of 2 or more types.
In addition, a metal salt, a metal complex, a metal alkoxide, and their content are demonstrated by the manufacturing method of the organic light emitting element 1 mentioned later.

Such an organic light emitting device 1 can be manufactured, for example, as follows. In addition, the description which overlaps with what was demonstrated above is abbreviate | omitted.
[1] First, the substrate 2 is prepared, and the anode 3 is formed on the substrate 2.
The anode 3 is, for example, a chemical vapor deposition method (CVD) such as plasma CVD, thermal CVD, or laser CVD, a dry plating method such as vacuum deposition, sputtering, or ion plating, or a wet method such as electrolytic plating, immersion plating, or electroless plating. It can be formed by using a plating method, a thermal spraying method, a sol-gel method, a MOD method, a metal foil bonding, or the like.

[2] Next, the hole transport layer 4 is formed on the anode 3.
The hole transport layer 4 is formed, for example, by supplying a hole transport layer forming material obtained by dissolving a hole transport material in a solvent or dispersing in a dispersion medium onto the anode 3 and then drying (desolvent or dedispersion medium). ).
Examples of the method for supplying the hole transport layer forming material include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, and spray coating. Various coating methods such as a printing method, a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method can be used. By using such a coating method, the hole transport layer 4 can be formed relatively easily.

Examples of the solvent or dispersion medium used for preparing the hole transport layer forming material include inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride, and ethylene carbonate, methyl ethyl ketone ( MEK), ketone solvents such as acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), cyclohexanone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG), glycerin, Diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether ( Grimm), ether solvents such as diethylene glycol ethyl ether (carbitol), cellosolv solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, toluene, xylene, Aromatic hydrocarbon solvents such as benzene, aromatic heterocyclic solvents such as pyridine, pyrazine, furan, pyrrole, thiophene, methylpyrrolidone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA Amide solvents such as chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane, ester solvents such as ethyl acetate, methyl acetate, ethyl formate, dimethyl sulfoxide (DMSO), sulfolane Various organic solvents such as sulfur compound solvents, nitrile solvents such as acetonitrile, propionitrile, acrylonitrile, organic acid solvents such as formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, or mixed solvents containing these Is mentioned.
The drying can be performed, for example, by standing in an atmospheric pressure or a reduced pressure atmosphere, heat treatment, or blowing an inert gas.

Prior to this step, the upper surface of the anode 3 may be subjected to oxygen plasma treatment. Thereby, it is possible to impart lyophilicity to the upper surface of the anode 3, remove (clean) organic substances adhering to the upper surface of the anode 3, adjust the work function near the upper surface of the anode 3, and the like. .
Here, the oxygen plasma treatment conditions include, for example, a plasma power of about 100 to 800 W, an oxygen gas flow rate of about 50 to 100 mL / min, a conveyance speed of the member to be treated (anode 3) of about 0.5 to 10 mm / sec, and a substrate. The temperature of 2 is preferably about 70 to 90 ° C.

[3] Next, the organic light emitting layer 5 is formed on the hole transport layer 4 (one surface side of the anode 3).
The organic light emitting layer 5 is dried (desolvent or dedispersion medium) after supplying an organic light emitting layer forming material obtained by dissolving a light emitting material in a solvent or dispersing in a dispersion medium onto the hole transport layer 4, for example. Can be formed.
The method for supplying the organic light emitting layer forming material and the method for drying are the same as described in the formation of the hole transport layer 4.

  In the case of using the light emitting material as described above, a nonpolar solvent is suitable as the solvent or dispersion medium used for preparing the organic light emitting layer forming material, for example, xylene, toluene, cyclohexylbenzene, dihydrobenzofuran, Aromatic hydrocarbon solvents such as trimethylbenzene and tetramethylbenzene, aromatic heterocyclic solvents such as pyridine, pyrazine, furan, pyrrole, thiophene and methylpyrrolidone, and aliphatic hydrocarbons such as hexane, pentane, heptane and cyclohexane Examples thereof include system solvents, and these can be used alone or as a mixed solvent containing them.

[4] Next, the electron transport layer 6 is formed on the organic light emitting layer 5.
(A) First Step First, a liquid material (liquid material) containing an organic-inorganic composite semiconductor containing the compound represented by the general formula (1) and metal ions as described above is prepared.
This is achieved by mixing a compound represented by the general formula (1) with at least one metal compound containing an alkali metal, an alkaline earth metal or a rare earth metal and a solvent, and dissociating metal ions from the metal compound. Can be prepared.

Alternatively, the compound represented by the general formula (1) and a solution of metal ions may be separately prepared and mixed. That is, you may mix and mix the 1st solution containing the compound represented by General formula (1), and the 2nd solution containing a metal compound. At this time, the solvents used in the respective solutions may be different as long as they can be mixed without being separated. This makes it possible to prepare a solution even when the solubility of the compound represented by the general formula (1) and the metal compound in a single solvent greatly changes and it is difficult to mix in a desired quantitative ratio. Become.
Furthermore, in any of the liquid material preparation methods, the above-mentioned B / A can be mixed so as to have a desired value, that is, a value similar to the value described for the liquid material. Thereby, the organic light emitting element 1 excellent in luminous efficiency and durability can be manufactured with high productivity.

  The metal compound is a compound having at least one metal ion of alkali metal ions, alkaline earth metal ions, or rare earth metal ions. For example, inorganic acid salts such as carbonates, nitrates and sulfates, acetates of alkali metals such as Li, Na and K, alkaline earth metals such as Mg, Ca and Sr or rare earth metals such as Yb, Sc and Y , Organic acid salts such as acetyl acetate, metal salts such as chlorides and halides such as bromides, metal alkoxides such as methoxide and ethoxide, metal complexes having detachable ligands such as acetylacetonate, etc. Is mentioned.

  More specifically, cesium carbonate, cesium acetate, cesium chloride, cesium acetylacetonate, lithium carbonate, lithium acetate, lithium chloride, lithium acetylacetonate, ytterbium carbonate, ytterbium acetate, ytterbium chloride, ytterbium acetylacetonate, calcium carbonate , Calcium acetate, calcium chloride, calcium acetylacetonate and the like.

Of these, it is preferable that at least one of them is a main component. In particular, cesium carbonate, cesium acetate, and chloride are preferable because they are relatively stable in the atmosphere, easy to handle, and easily dissociate metal ions. Cesium, ytterbium chloride, calcium chloride, and lithium acetylacetonate are preferable. Thereby, it is possible to produce an organic semiconductor element that is excellent in high efficiency and durability, and has a high electron injection property and a high electron transport property with higher productivity.
The content of the metal compound in the electron transport layer 6 is preferably 1 to 30 wt% with respect to the constituent material of the electron transport layer 6.

As the solvent used for preparing the liquid material containing the organic-inorganic composite semiconductor material, a solvent that does not easily swell or dissolve the organic light emitting layer 5 is preferable. Thereby, it is possible to prevent the light emitting material from being altered or deteriorated, or the organic light emitting layer 5 from being dissolved and the film thickness from being extremely reduced. As a result, it is possible to prevent a decrease in the light emission efficiency of the organic light emitting device 1.
Furthermore, when preparing this solvent and the solution of the compound represented by the general formula (1) and the metal compound separately, the solvent used for the solution of the metal compound dissolves the metal compound and dissociates metal ions. Is preferred.
In consideration of the above, it is preferable to use a protic polar solvent as the solvent. Thereby, the fall of luminous efficiency can be prevented and the organic light emitting element 1 can be manufactured with high productivity.

  Examples of the protic polar solvent include water, methanol, ethanol, propanol, butanol, benzyl alcohol, monovalent alcohols such as diethylene glycol monomethyl ether, alcohols such as polyhydric alcohols such as ethylene glycol and glycerin, acetic acid, formic acid, ( Carboxylic acids such as (meth) acrylic acid, amines such as ethylenediamine and diethylamine, formamide, amides such as N, N-dimethylformamide, phenols, phenols such as p-butylphenol, acetylacetone, diethyl malonate Such active methylene compounds and the like can be mentioned, and one or more of these can be used in combination.

  Especially, as a protic polar solvent, what has at least 1 sort (s) of water and alcohol as a main component is preferable. Since water and alcohols have high solubility of metal compounds, the use of a protic polar solvent that contains at least one of water and alcohols as a main component ensures that metal ions are extracted from the metal compounds. The liquid material containing the organic-inorganic composite semiconductor material can be easily prepared.

In particular, the alcohol is preferably a monohydric alcohol having 1 to 7 carbon atoms (preferably 1 to 4 carbon atoms). Such a monohydric alcohol having a carbon number has high solubility of the metal compound.
For example, when dissolved cesium carbonate as a metal compound _(Cs 2 CO ₃₎ in the unit price alcohol (R-OH), by the following reactions, Cs ions (metal ions) are believed to dissociate.

Cs ₂ CO ₃ + 2ROH → 2Cs (OR) + CO ₂ + H ₂ O
Cs (OR) + H ₂ O → Cs ⁺ + OH ⁻ + ROH
In addition, in the liquid material containing the organic-inorganic composite semiconductor material, the compound represented by the general formula (1) and the metal compound are converted into the compound represented by the general formula (1) in the obtained electron transport layer 6. The number A [number] of P = O bonds included and the number B [number] of metal ions are as described above, and B / A is preferably 0.05 or more, more preferably 0.2. Preferably, it is 0.2 to 1.5. Thereby, it is possible to manufacture the organic light emitting device 1 that is further excellent in light emission efficiency and durability, and has a high electron injection property and a high electron transport property with higher productivity.

For example, the case where the compound represented by the following chemical formula 12 is used as the compound represented by the general formula (1), Cs ₂ CO ₃ is used as the metal compound, and B / A is 0.2 will be described.
The compound represented by Chemical formula 12 contains 4 P═O bonds. On the other hand, _two Cs ions are dissociated from Cs ₂ CO ₃ . For this reason, in order to set B / A to 0.2, 0.4 mol of Cs ₂ CO ₃ may be mixed with 1 mol of the compound shown in Chemical formula 12.

(B) 2nd process Next, after supplying the liquid material containing the prepared organic inorganic composite semiconductor material on the organic light emitting layer 5, it dries (desolves). Thereby, the electron carrying layer 6 comprised with an organic inorganic composite semiconductor material is obtained.
The method for supplying the liquid material containing the organic-inorganic composite semiconductor material and the method for drying are the same as described in the formation of the hole transport layer 4.

[5] Next, the cathode 7 is formed on the electron transport layer 6 (on the side opposite to the organic light emitting layer 5).
(C) Third Step This step is a step of forming a cathode on the side of the electron transport layer 6 opposite to the organic light emitting layer 5.
The cathode 7 can be formed by using, for example, a vacuum deposition method, a sputtering method, bonding of metal foil, application and firing of metal fine particle ink, or the like.
Through the steps as described above, the organic light emitting device 1 is obtained.
Finally, the sealing member 8 is covered so as to cover the obtained organic light emitting device 1 and bonded to the substrate 2.

According to the manufacturing method as described above, a vacuum apparatus or the like can be used for forming an organic layer (hole transport layer 4, organic light emitting layer 5, electron transport layer 6), or for forming a cathode 7 when using metal fine particle ink. Therefore, the manufacturing time and manufacturing cost of the organic light emitting device 1 can be reduced. In addition, by applying an ink jet method (droplet discharge method), it is easy to fabricate a large-area element and to apply multiple colors.
In the present embodiment, the hole transport layer 4 and the organic light emitting layer 5 are described as being manufactured by a liquid phase process. However, in the present invention, depending on the type of the hole transport material and the light emitting material to be used, The layer may be formed by, for example, a gas phase process such as a vacuum deposition method.

Such an organic light emitting device 1 can be used as a light source, for example. Moreover, a display apparatus (light-emitting device of this invention) can be comprised by arrange | positioning the some organic light emitting element 1 in matrix form.
The driving method of the display device is not particularly limited, and may be either an active matrix method or a passive matrix method.

Next, an example of a display device to which the light emitting device of the present invention is applied will be described.
FIG. 2 is a longitudinal sectional view showing an embodiment of a display device to which the light emitting device of the present invention is applied.
A display device 10 shown in FIG. 2 includes a base body 20 and a plurality of organic light emitting elements 1 provided on the base body 20.

The base body 20 includes a substrate 21 and a circuit unit 22 formed on the substrate 21.
The circuit unit 22 includes a protective layer 23 made of, for example, a silicon oxide layer formed on the substrate 21, a driving TFT (switching element) 24 formed on the protective layer 23, a first interlayer insulating layer 25, And a second interlayer insulating layer 26.
The driving TFT 24 includes a semiconductor layer 241 made of silicon, a gate insulating layer 242 formed on the semiconductor layer 241, a gate electrode 243 formed on the gate insulating layer 242, a source electrode 244, and a drain electrode 245. have.
The organic light emitting element 1 is provided on the circuit portion 22 corresponding to each driving TFT 24. Adjacent organic light emitting elements 1 are partitioned by a first partition wall 31 and a second partition wall 32.

In the present embodiment, the anode 3 of each organic light emitting element 1 constitutes a pixel electrode and is electrically connected to the drain electrode 245 of each driving TFT 24 by the wiring 27. Further, the cathode 7 of each organic light emitting element 1 is a common electrode.
And the sealing member (not shown) is joined to the base | substrate 20 so that each organic light emitting element 1 may be covered, and each organic light emitting element 1 is sealed.
The display device 10 may be monochromatic display, and color display is also possible by selecting a light emitting material used for each organic light emitting element 1.
Such a display device 10 (the light emitting device of the present invention) can be incorporated into various electronic devices.

FIG. 3 is a perspective view showing the configuration of a mobile (or notebook) personal computer to which the electronic apparatus of the present invention is applied.
In this figure, a personal computer 1100 includes a main body 1104 provided with a keyboard 1102 and a display unit 1106 provided with a display. The display unit 1106 is rotatable with respect to the main body 1104 via a hinge structure. It is supported by.
In the personal computer 1100, the display unit included in the display unit 1106 is configured by the display device 10 described above.

FIG. 4 is a perspective view showing a configuration of a mobile phone (including PHS) to which the electronic apparatus of the present invention is applied.
In this figure, a cellular phone 1200 includes a plurality of operation buttons 1202, an earpiece 1204 and a mouthpiece 1206, and a display unit.
In the mobile phone 1200, the display unit is configured by the display device 10 described above.

FIG. 5 is a perspective view showing a configuration of a digital still camera to which the electronic apparatus of the present invention is applied. In this figure, connection with an external device is also simply shown.
Here, an ordinary camera sensitizes a silver halide photographic film with a light image of a subject, whereas a digital still camera 1300 photoelectrically converts a light image of a subject with an imaging device such as a CCD (Charge Coupled Device). An imaging signal (image signal) is generated.

A display unit is provided on the back of a case (body) 1302 in the digital still camera 1300, and is configured to display based on an imaging signal from the CCD, and functions as a finder that displays an object as an electronic image.
In the digital still camera 1300, the display unit is configured by the display device 10 described above.

A circuit board 1308 is installed inside the case. The circuit board 1308 is provided with a memory that can store (store) an imaging signal.
A light receiving unit 1304 including an optical lens (imaging optical system), a CCD, and the like is provided on the front side of the case 1302 (on the back side in the illustrated configuration).
When the photographer confirms the subject image displayed on the display unit and presses the shutter button 1306, the CCD image pickup signal at that time is transferred and stored in the memory of the circuit board 1308.

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

  The electronic apparatus of the present invention includes, for example, a television, a video camera, a viewfinder type, in addition to the personal computer (mobile personal computer) in FIG. 3, the mobile phone in FIG. 4, and the digital still camera in FIG. Monitor direct-view video tape recorder, laptop personal computer, car navigation system, pager, electronic notebook (including communication function), electronic dictionary, calculator, electronic game device, word processor, workstation, video phone, security TV Monitors, electronic binoculars, POS terminals, devices equipped with touch panels (for example, cash dispensers and automatic ticket vending machines for financial institutions), medical devices (for example, electronic thermometers, blood pressure monitors, blood glucose meters, electrocardiographs, ultrasound diagnostic devices, internal Endoscope display device), fish finder, various measuring instruments, Vessels such (e.g., gages for vehicles, aircraft, and ships), a flight simulator, various monitors, and a projection display such as a projector.

Above, the organic-inorganic composite semiconductor material of the present invention, the liquid material, an organic light emitting device, a light emission device and an electronic apparatus, has been described with reference to the illustrated embodiments, the present invention is not limited thereto.
For example, in the organic light-emitting device of the present invention, one or more desired layers can be provided in at least one of the layers.

Next, specific examples of the present invention will be described.
1. Production of organic light emitting device (Example 1)
<1> First, a transparent glass substrate having an average thickness of 0.5 mm was prepared.
<2> Next, an ITO electrode (anode) having an average thickness of 100 nm was formed on the substrate by sputtering.
And the board | substrate was immersed in order of acetone and 2-propanol, and ultrasonically cleaned.

<3> Next, an aqueous dispersion of poly (3,4-ethylenedioxythiophene / styrenesulfonic acid) (PEDOT / PSS) was applied on the ITO electrode by a spin coating method, and then heated to 200 ° C. Dry on a hot plate for 10 minutes at atmospheric pressure. Thereby, a hole transport layer having an average thickness of 60 nm was formed.
<4> Next, a monochlorobenzene solution in which polyvinyl carbazole and factory (2-phenylpyridine) iridium were dissolved was applied on the hole transport layer by a spin coating method and then dried. Thereby, an organic light emitting layer having an average thickness of 70 nm was formed.
The mixing ratio of polyvinyl carbazole and factory (2-phenylpyridine) iridium was 97: 3 by weight.

<5> First, cesium carbonate (Cs ₂ CO ₃ ) was dissolved in 2-propanol as a metal compound. Next, this solution was added to 4,4 ′, 4 ″ -tris (diphenylphosphinyl) -triphenylphosphine oxide (hereinafter abbreviated as “TPPO-Burst”), and then the concentration of TPPO-Burst was increased. It diluted with 2-propanol so that it might become 0.5 wt%. Thereby, an electron transport layer forming material was obtained.

The mixing ratio of TPPO-Burst and cesium carbonate was 2: 1 in terms of molar ratio. That is, the B / A was set to 0.25.
The prepared material for forming an electron transport layer was applied on the organic light emitting layer by a spin coating method, and then dried for 10 minutes in a nitrogen atmosphere on a hot plate heated to 130 ° C. Thereby, an electron transport layer having an average thickness of 15 nm was formed.

<6> Next, an Al electrode (cathode) having an average thickness of 200 nm was formed on the electron transport layer by vacuum deposition.
Next, a glass protective cover (sealing member) was placed over the formed layers, and fixed and sealed with an epoxy resin.

(Example 2)
In the step <5>, except that the blending ratio of TPPO-Burst (compound shown in Chemical formula 12) and cesium carbonate was 10: 1 in molar ratio and B / A was 0.05, In the same manner as in Example 1, an organic light emitting device was manufactured.
(Example 3)
In the step <5>, except that the blending ratio of TPPO-Burst (compound shown in Chemical formula 12) and cesium carbonate was 5: 1 in molar ratio, and the B / A was 0.1, In the same manner as in Example 1, an organic light emitting device was manufactured.

Example 4
In the step <5>, except that the mixing ratio of TPPO-Burst (compound shown in Chemical formula 12) and cesium carbonate was 1: 1 in terms of molar ratio, and the B / A was 0.5. In the same manner as in Example 1, an organic light emitting device was manufactured.
(Example 5)
In the step <5>, except that the blending ratio of TPPO-Burst (compound shown in Chemical formula 12) and cesium carbonate was 1: 2 in molar ratio, and the B / A was 1.0, In the same manner as in Example 1, an organic light emitting device was manufactured.

(Example 6)
In the step <5>, lithium acetylacetonate (Li (acac)) is used as the metal compound, and the mixing ratio of TPPO-Burst (compound shown in Chemical formula 12) and lithium acetylacetonate is 1: 1 by molar ratio. Then, an organic light emitting device was manufactured in the same manner as in Example 1 except that the B / A was 0.25.

(Example 7)
In the step <5>, cesium chloride is used as the metal compound, the blending ratio of TPPO-Burst (compound shown in Chemical formula 12) and cesium chloride is 1: 1 at a molar ratio, and the B / A is 0.25. An organic light emitting device was manufactured in the same manner as in Example 1 except that the above was obtained.

(Example 8)
In the step <5>, cesium acetate is used as the metal compound, the blending ratio of TPPO-Burst (compound shown in Chemical formula 12) and cesium acetate is 1: 1, and the B / A is 0.25. An organic light emitting device was manufactured in the same manner as in Example 1 except that the above was obtained.

Example 9
In the step <5>, calcium chloride (CaCl ₂ ) is used as the metal compound, and the blending ratio of TPPO-Burst (compound shown in Chemical formula 12) and calcium chloride is 1: 1 at a molar ratio, and the B / A The organic light emitting device was manufactured in the same manner as in Example 1 except that the value of 0.25 was 0.25.

( Reference example )
In step <5>, ytterbium chloride (YbCl ₃ ) is used as the metal compound, and the blending ratio of TPPO-Burst (compound shown in Chemical formula 13) and ytterbium chloride is 1: 1 in terms of a molar ratio. An organic light emitting device was manufactured in the same manner as in Example 1 except that A was 0.25.

(Comparative Example 1)
An organic light-emitting device was manufactured in the same manner as in Example 1 except that in the step <5>, blending of cesium carbonate was omitted.
(Comparative Example 2)
In the step <5>, except that the B / A of cesium carbonate and TPPO-Burst (compound shown in Chemical formula 12) was 0.05 and co-evaporated to form an electron transport layer In the same manner as in Example 1, an organic light emitting device was produced.
The ratio of TPPO-Burst (compound shown in Chemical formula 12) to cesium carbonate was 2: 1 in terms of molar ratio.

2. Evaluation 2-1. Confirmation of the presence of metal ions In each of the examples , reference examples, and comparative examples, before forming the Al electrode, the electronic state of the metal present in the electron transport layer was measured by X-ray photoelectron spectroscopy (XPS method). ).
This X-ray photoelectron spectroscopic analysis was performed using an XPS apparatus (manufactured by PHI, “Quantera SXM”).
As a result, the presence of metal ions could be confirmed in each of the electron transport layers in Examples and Reference Examples .

2-2. Evaluation of luminous efficiency A voltage of 8 V was applied from the DC power source between the anode and the cathode to the organic light emitting devices manufactured in each of the examples , reference examples and comparative examples, and the current value and luminance at this time Was measured. From these values, the luminous efficiency [cd / A] was determined.
2-3. Durability Evaluation With respect to the organic light emitting devices manufactured in each of the examples , reference examples, and comparative examples, a voltage was applied from a DC power source between the anode and the cathode, and a constant current with an initial luminance of 400 Cd / m ² was obtained. Driven. And the period (half-life) when a brightness | luminance becomes half of the initial stage was calculated | required.
The evaluation results of 2-2 (evaluation of luminous efficiency) and 2-3 (evaluation of durability) are shown in Table 1 below.

In Table 1, for each evaluation result, Examples 1 to 9 and Reference Example are shown as relative values when Comparative Examples 1 and 2 are set to “1”.
As shown in Table 1, each of the organic light-emitting devices produced in each example and reference example was excellent in luminous efficiency and durability.
On the other hand, all of the organic light emitting devices manufactured in the respective comparative examples were inferior in light emission efficiency and durability of the organic light emitting device of the present invention.

It is a figure which shows typically the longitudinal cross-section of embodiment of the organic light emitting element of this invention. It is a longitudinal cross-sectional view which shows embodiment of the display apparatus to which the light-emitting device of this invention is applied. 1 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which an electronic apparatus of the present invention is applied. It is a perspective view which shows the structure of the mobile telephone (PHS is also included) to which the electronic device of this invention is applied. It is a perspective view which shows the structure of the digital still camera to which the electronic device of this invention is applied.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Organic light emitting element 2 ... Substrate 3 ... Anode 4 ... Hole transport layer 5 ... Organic light emitting layer 6 ... Electron transport layer 7 ... Cathode 8 ... Sealing member 10 ... Display device 20 ... ... Substrate 21 ... Substrate 22 ... Circuit part 23 ... Protective layer 24 ... Driving TFT 241 ... Semiconductor layer 242 ... Gate insulating layer 243 ... Gate electrode 244 ... Source electrode 245 ... Drain electrode 25 ... ... first interlayer insulating layer 26 ... second interlayer insulating layer 27 ... wiring 31 ... first partition part 32 ... second partition part 1100 ... personal computer 1102 ... keyboard 1104 ... main body part 1106 ... display Unit 1200 ... mobile phone 1202 ... operation buttons 1204 ... earpiece 1206 ... mouthpiece 1300 ... digital still camera 1302 ... Case (body) 1304 ...... light receiving unit 1306 ...... shutter button 1308 ...... circuit board 1312 ...... video signal output terminal 1314 input-output terminal 1430 ...... television monitor 1440 ...... personal computer ...... for data communication

Claims (2)

A compound represented by the following general formula (1) (wherein Ar ¹ , Ar ² and Ar ³ have at least an aromatic ring group);
A metal salt having at least one metal ion of alkali metal ions and alkaline earth metal ions;
A protic polar solvent;
Including
The metal salt is dissociated by dissolving in the protic polar solvent ,
When the number of P═O bonds contained in the compound represented by the general formula (1) is A [number] and the number of the metal ions is B [number], the compound is represented by the general formula (1). B / A, which is the ratio of the amount of the compound and the metal ion, is 0.2 to 1.5.

The liquid material according to claim 1 , wherein the alkali metal ion is a Cs ion, and the alkaline earth metal ion is a Ca ion.

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