JPH0660983A - Organic thin electroluminescence element - Google Patents

Abstract

PURPOSE:To intensify emission intensity further, and realize a practical level of high durability by specifying a substrate temperature when an element is manufactured and an organic layer containing an emission layer. CONSTITUTION:A comb shape anode 2 is arranged on a glass substrate 1, and an organic laminate layer body 7 is arranged to cover the anode 2. A comb shape cathode 3 is arranged in a grid shape to the anode 2, and an anode lead wire Ip and a cathode lead wire In are connected to respective poles. Next, this constitutive body is embedded in a case C, and next, an inactive material S is filled fully in the case, and air is discharged, and this upper part is covered and sealed from above with a transparent roof plate T, and an element is formed. When it is manufacture, a vacuum evaporation method is applied, and a film is formed within range of a substrate temperature of -l0 deg.C--196 deg.C when it is manufactured. An organic layer 7 is formed by providing a layer containing an organic compound expressed by a specific formula and a layer containing a styryl compound expressed by a specific formula respectively by at least one or more layers apiece.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin film electroluminescent device, and more particularly to an organic thin film electroluminescent device used for flat light sources and flat displays.

[0002]

2. Description of the Related Art An electroluminescence device is composed of an organic light emitting layer and a pair of counter electrodes sandwiching the organic light emitting layer, and the emitted light is injected from one electrode and the other electrode. The holes recombine in the light-emitting layer to excite the light-emitting body to a higher energy level, and the excited light-emitting body emits energy as light when returning to the original ground state.
In such a carrier injection type electroluminescence element, since a thin film organic compound is used as a light emitting layer, one having a high light emission intensity has been obtained. For example, U.S. Pat. No. 3,530,325 uses a single crystal anthracene or the like as a light emitter, and JP-A-59-194393 discloses a combination of a hole injection layer and an organic light-emitting layer.
63-295695 is a combination of a hole injection transport layer and an organic electron injection transport layer, and Jpn. Journal of Applied Physics, v.
ol27, No2, P269-271 discloses a combination of a hole transfer layer, a light emitting layer, and an electron transfer layer, and the emission intensity has been improved so far.

However, in the conventional electroluminescence device having the above-mentioned structure, although the emission intensity has been improved, there is a problem in durability, and the emission intensity and durability of a practical level have not yet been reached. Therefore,
It has been desired to develop an electroluminescence device having higher emission intensity and higher durability.

Further, Japanese Patent Laid-Open Nos. 57-51781 and 59-194393 disclose a method of making a substrate. However, since the temperature of the substrate at the time of making is room temperature, a hole injection layer, an organic light emitting layer, etc. Since the organic layer had remarkable aggregation and crystallinity, it was not possible to maintain practical performance.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a practical level organic thin film electroluminescent device having higher emission intensity and higher durability. .

[0006]

The above-mentioned object of the present invention is a vacuum vapor deposition method for producing an organic thin film electroluminescent device comprising at least an electrode and an upper electrode provided on a transparent substrate, and the substrate temperature at the time of production is -10 ° C. This can be achieved by an organic thin film electroluminescent element formed in the range of ˜-196 ° C. and its manufacturing method. If the temperature is -10 ° C or higher, the aggregation and crystallization of the organic layer cannot be suppressed, and if the temperature is -196 ° C or lower, it cannot be reached by liquid nitrogen alone. Further, the emission brightness of the device is significantly changed due to the amorphous change, and the durability is deteriorated. In the vacuum vapor deposition method, a film is formed by keeping the substrate humidity at a constant temperature by using a refrigerant such as liquid nitrogen, liquid helium, or dry ice together with a heater.
Further, in the organic thin film electroluminescent device, at least one layer containing an organic compound represented by the following general formula [I] and a layer containing a styryl compound represented by the following general formula [II] is provided. This is achieved by the organic thin film electroluminescent elements provided separately.

In a preferred embodiment, the following general formula [I]
The organic compound represented by
The organic thin film electroluminescent device as described above, wherein the styryl compound represented by the formula [I] is used as a hole transport material.

[0008]

[Chemical 3]

(Z1) of the residue Z of the general formula [I]
In (Z4), R _{1 to} R ₁₁ are each independently a hydrogen atom,
Halogen atom, substituted or unsubstituted 5 groups; alkyl group, monovalent group derived from unsaturated chain hydrocarbon, heterocyclic group, aryl group, group containing 2 or more nitrogen atoms, or styryl group , Anisyl group, amino group, alkylamino group, dialkylamino group, alkoxy group, alkoxycarbonyl group, aminocarbonyl group, aryloxycarbonyl group, carboxyl group, acyl group, aryloxyl group, aralkyl group, acylamino group, acyloxyl group Represents a hydroxyl group, a cyano group, a nitro group, a sulfo group, and a sulfonium group, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₆
And R ₇ , R ₇ and R ₈ , R ₈ and R ₉ , R ₉ and R ₁₀ , and R ₁₀ and R ₁₁ may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring structure. Good.

Further, (Z5) of the residue Z of the above general formula [I]
Inside X represents a substituted or unsubstituted heterocycle.

[0011]

[Chemical 4]

Further, in the above general formula [II], in the formula, R ₁₂ and R
₁₃ are each independently a hydrogen atom, a substituted or unsubstituted four groups described below; an alkyl group, a heterocyclic group, an aryl group,
Represents a monovalent group derived from an unsaturated chain hydrocarbon, R
₁₂ and R ₁₃ may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring structure.

R ₁₄ is the following three groups which are substituted or unsubstituted; an alkyl group, an aryl group, an alkoxy group, or
_{{P (C 6 H 4)} } - CH = C {(- R 12) (- R 13)} represents, R ₁₂ and R ₁₃ are as defined above.

R ₁₅ represents a hydrogen atom, the following three substituted or unsubstituted groups; an alkyl group, an aryl group and an alkoxy group.

Residues (Z-1) to (Z- of the general formula [I]
5) and the halogen atom represented by the general formula [II] is a halogen atom such as chlorine atom, bromine atom, fluorine atom and iodine atom; the substituted or unsubstituted alkyl group is methyl group, ethyl group, propyl group, butyl. Groups, alkyl groups such as cyclohexyl groups; vinyl groups as monovalent groups derived from substituted or unsubstituted unsaturated chain hydrocarbons,
Monovalent groups derived from unsaturated chain hydrocarbons such as 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 2-pentenyl group, ethynyl group; substituted or unsubstituted The heterocyclic group of is a piperidyl group, a piperidino group, a pyrrolyl group, a furyl group, a cenyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a pyridyl group, a thiazolyl group, a pyridazinyl group, a monovalent group consisting of pyridone, and a morpholinyl group. , Heteromorphic groups such as morpholino group, oxazolyl group, isoxazolyl group, isothiazolyl group, pyrimidinyl group, pyrazinyl group, pyranyl group, benzimidazolyl group, benzothiazolyl group, benzoxazolyl group, quinolyl group; substituted or unsubstituted aryl group Are phenyl group, naphthyl group, antonyl group, xylyl group, Aryl groups such as phenyl group and phenanthryl group; Substituted or unsubstituted groups containing two or more nitrogen atoms are azo group, phenylazo group, naphthyrazo group, hydranizo group, hydrazo group, azoxy group, azido group, diazoamino group, amidino group , A group containing two or more nitrogen atoms such as a ureylene group and a guanidino group; an alkoxyl group such as a methoxyl group, an ethoxyl group, a propoxyl group, a butoxyl group, a pentyloxyl group, a hexyloxyl group; an alkoxycarbonyl group Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and butoxycarbonyl group; aminocarbonyl groups such as anilinocarbonyl group, dimethylaminocarbonyl group, larvamoyl group and alanyl group; Aryloxycarbonyl groups such as naphthyloxycarbonyl group, xylyloxycarbonyl group and phenoxycarbonyl group as ruoxycarbonyl group; formyl group, acetyl group, propionyl group, butyryl group, pareryl group, oaluminoyl group, stearoyl as acyl group Groups, acyl groups such as oleoyl group, benzoyl group, trioyl group, salicyloyl group, cinnamoyl group, naphthoyl group, phthaloyl group, oxalyl group, malonyl group, succinyl group, furoyl group; phenoxy group and tolyloxy group as aryloxyl group Aryloxyl groups such as; aralkyl groups such as benzyl and phenethyl groups; acylamino groups such as acetylamino, propionylamino and butyrylamino groups; Shiruokishiru The group acetyloxy group,
An acyloxyl group such as a propionyloxy group and a butyryloxy group.

The above-mentioned substituents include hydrogen atom, halogen atom, alkyl group such as methyl group, ethyl group, propyl group, butyl group and cyclohexyl group, vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-
Monovalent groups derived from unsaturated chain hydrocarbons such as butenyl group, 2-pentenyl group, ethynyl group, piperidyl group,
Piperidino group, pyrrolyl group, furyl group, cenyl group,
Monovalent group consisting of imidazolyl group, pyrazolyl group, triazolyl group, pyridyl group, thiazolyl group, pyridazinyl group, pyridone, morpholinyl group, morpholino group, oxazolyl group, isoxazolyl group, isothiazolyl group, pyrimidinyl group, pyrazinyl group, pyranyl group, Heterocyclic groups such as benzimidazolyl group, benzothiazolyl group, benzoxazolyl group, quinolyl group, phenyl group, naphthyl group, antonyl group, aryl groups such as xylyl group, biphenyl group, phenanthryl group, azo group, phenylazo group, naphthyrazo group Groups, hydranizo groups, hydrazo groups, azoxy groups, azido groups, diazoamino groups, groups containing two or more nitrogen atoms such as amidino groups, ureylene groups, guanidino groups, styryl groups, anisyl groups, amino groups, alkylamino groups, dialkyl groups. Group, methoxyl group, ethoxyl group, propoxyl group, butoxyl group, pentyloxyl group, hexyloxyl group and other alkoxy groups, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and other alkoxycarbonyl groups, anilinocarbonyl group, Aminocarbonyl groups such as dimethylaminocarbonyl group, larvamoyl group, alanyl group, naphthyloxycarbonyl group, xylyloxycarbonyl group, aryloxycarbonyl group such as phenoxycarbonyl group, carboxyl group, formyl group, acetyl group, propionyl group, butyryl Group, pareryl group, oaluminoyl group, stearoyl group, oleoyl group, benzoyl group, trioyl group, salicyloyl group, cinnamoyl group, naphthoyl group, phthaloyl group, oxalyl group, malo Group such as acyl group, succinyl group and furoyl group, aryloxy group such as phenoxy group and tolyloxy group, aralkyl group such as benzyl group and phenethyl group, acylamino group such as acetylamino group, propionylamino group and butyrylamino group, acetyl It represents an acyloxyl group such as an oxy group, a propionyloxy group and a butyryloxy group, a hydroxyl group, a cyano group, a nitro group, a sulfo group or a sulfonium group.

Specific examples of such an organic compound represented by the general formula [I] are described in, for example, the specification of Japanese Patent Application No. 3-333517.

Next, specific examples of the styryl compound represented by the general formula [II] are described in, for example, Japanese Patent Application No. 3-333517.

The organic compound represented by the general formula [I] of the present invention can be easily synthesized by a known method (described in J. Chem. Soc, 1957, 4616, etc.).

Synthesis Example 1 The styryl compound represented by the general formula [II] is obtained by reacting a phosphorus compound represented by the following general formula [III] with a diformyl compound represented by the general formula [IV]. You can

[0021]

[Chemical 5]

In the general formula [III], R ₁₂ and R ₁₃ have the same meanings as [II], and X is a triphenylphosphonium group or a trialkylphosphonium salt represented by -P ⁺ -(R ₁₆ ) ₃ Y-. , Or a dialkyl phosphite group represented by —PO (OR ₁₇ ) ₂ . R ₁₆ represents an alkyl group or an aryl group, and Y
Represents a halogen ion, and R ₁₇ represents an alkyl group.

In the general formula [IV], R ₁₄ and R ₁₅ have the same meanings as [II].

The phosphorus compound represented by the general formula [III] can be easily prepared by heating the corresponding halomethyl compound and triarylphosphine or trialkylsulfin, or trialkyl phosphite directly or in a solvent such as toluene or xylene. Can be manufactured.

As a reaction solvent in the method for synthesizing the styryl compound, an inert solvent such as hydrocarbons, alcohols and ethers is preferable, and methanol, ethanol, isopropanol, butanol, 2-methoxyethanol, 1,2-dimethoxy are preferable. Ethane, bis (2-methoxyethyl) ether, dioxane, tetrahydrofuran, toluene, xylene, dimethylsulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-
Examples include imidazolidinone. Among them, polar solvents,
For example, N, N-dimethylformamide and dimethyl sulfoxide are suitable.

Alcolates such as caustic soda, caustic potash, sodium sodium amide hydride and sodium methylate, potassium t-butoxide, etc. are used as the condensing agent. The reaction temperature is about 0 depending on the stability of the solvent used for the condensing agent, the reactivity of the condensation component, and the reactivity of the condensing agent.
A wide range can be selected from 0 ° C to about 100 ° C, preferably 10 to 80 ° C.

Next, the present invention will be described in detail.

First, the production of the organic thin film electroluminescent element of the present invention will be described with reference to FIG.

FIG. 1 (1) shows a state in which a comb-shaped anode 2 is provided on a glass substrate 1, and FIG. 1 (2) shows an organic laminate 7 having a light-emitting function provided covering the anode 2. In (3), the comb-shaped cathode 3 is further provided in a grid pattern with respect to the anode 2, and the anode lead wire lp and the cathode lead wire ln are connected to the respective poles. Next, the case C is fitted into the above-mentioned structure (Fig. 4 (4)), and then the inactive substance S is filled to the full extent of the case C, and air is evacuated on the case C and covered with a transparent top plate T (see the same figure). (5)) completes.

Although the layer structure of the organic thin film electroluminescence element of the present invention has various modes, it is basically composed of an organic laminate layer having a light emitting function and a pair of counter electrodes sandwiching the layer. In the present invention, the p-layer and / or the n-layer are essentially provided. A specific example is shown in FIG. Substrate / anode / p layer / light emitting layer / cathode (FIG. 2 (1)), substrate / anode / light emitting layer / n layer / cathode (FIG. 2 (2)), substrate / anode / p layer / light emitting layer / n layer / Cathode (FIG. 2 (3)) and the like, but the present invention is not necessarily limited to this structure, and each of them may be provided with a plurality of light emitting layers, p layers, and n layers, or each may be a p layer. / Emissive layer, emissive layer / n layer, p layer / emissive layer / n layer are repeatedly laminated, or a mixed layer of an electron injection material and a light emitting material between the emissive layer and the n layer, p layer and light emission A mixed layer of a hole injection material and a light emitting material may be provided between the layers, or another layer may be provided in each layer.

The organic layer can be formed by a vapor deposition method, a spin coating method, a casting method or the like, but the vacuum vapor deposition layer is most desirable in terms of characteristics, and the thickness of the light emitting layer is preferably 2 to 100 nm, more preferably 5 to 20 nm. Is. The p-layer thickness is 10 ~
200 nm is preferable, and 20 to 100 nm is more preferable. n
The layer thickness is preferably 10 to 200 nm, more preferably 20 to 1
It is 00 nm.

The substrate 1 is made of, for example, soda glass, non-fluorescent glass, phosphoric acid type glass, boric acid type glass or the like, metal plate or metal foil such as quartz or alumina, acrylic resin, styrene resin, polycarbonate resin, A plastic plate or plastic film made of epoxy resin, polyethylene, polyester or silicone resin, a metal plate made of alumina or metal foil, or the like is used.

The anode 2 preferably has a work function larger than 4 eV, such as carbon, aluminum, vanadium,
Metals such as iron, cobalt, nickel, chromium, copper, zinc, tungsten, silver, tin, platinum and gold and their alloys, tin oxides such as zinc oxide, indium oxide, ITO and NESA or indium tin oxide-based composites Compounds, compounds such as copper iodide, mixtures of oxides and metals such as ZnO: Al, SnO ₂ : Sb, and inductive polymers such as poly (3-methylthiophene), polypyrrole and polyaniline are used. The film thickness is preferably 10 to 1000 nm,
More preferably, it is 10 to 200 nm.

The cathode 3 preferably has a work function smaller than 4 eV, and is made of magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, ytterbium, ruthenium, manganese, aluminum, silver, tin or lead. Metals and alloys thereof, aluminum / aluminum oxide composites and the like are used. The film thickness is preferably 10 to 1000 nm,
More preferably, it is 10 to 900 nm.

When light is taken out from the electrode, at least one of the anode 2 and the cathode 3 is transparent or semitransparent with a transmittance of 10% or more, and only the anode 2 is transparent or semitransparent with a transmittance of 10% or more. When it is transparent, the substrate 1 is also preferably transparent or semi-transparent.

The present invention can also use the following inert substances.

Mineral oil type insulating oil (transformer oil, condenser oil, power cable oil) Example: ASTM DI040, WEMCO-C CSA C50 IEC-296 BS148, J
ISC2320 ・ Synthetic insulating oil Examples: alkylbenzene, polybutene, diallylethane,
Alkylnaphthalene, o-olefin, phosphoric acid ester, carboxylic acid ester, silicone, siloxane, diphenyl pentachloride, diphenyl trichloride, fluorine oil, sulfonated oil,
Ethers, sulfonates, liquid paraffin, paraffin It is preferable that the inert substance does not pass water or oxygen.

As the material used for the case, a resin that is transparent to ordinary visible rays is used.

Examples of the resin include ethylene-vinyl alcohol copolymer, vinylidene chloride-methyl acrylate copolymer, polyethylene-isophthalate copolymer, terephthalic acid-isophthalic acid-hexamethylenediamine copolymer, polyacrylonitrile resin, poly -p-phenylene terephthalamide, polyprene, poly-4-methylpentene-1, polyester, polyetherimide,
Polycarbonate, polyarylate, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene Examples thereof include copolymers, polyvinylidene fluoride, polyvinyl fluoride, polysulfone, butyral resin, aromatic nylon, polyphenylene sulfide, polyether ether ketone, cellophane, and styrene.

Further, those described in "Revised 3rd Edition Engineering Plastics Chemical Industry Daily" and those described in "New packaging material Kyoritsu Publishing" are referred to.

Next, the hole injecting compound having a hole transporting ability used for the p layer 5 will be described. Specific examples of the hole injection compound include, for example, triazole derivatives (US Pat.
3,112,197), oxadiazole derivatives (also described in US Pat. No. 3,189,447), imidazole derivatives (described in Japanese Patent Publication No. 37-16096), polyarylalkane derivatives (US Pat. No. 3,615). , 40
No. 2, No. 3,820,989, No. 3,542,544, Japanese Patent Publication No. 45-555
No. 51-10983, JP-A-51-93224, 55-17105,
56-4148, 55-108667, 56-36656, 55-156
953), pyrazoline derivatives and pyrazolone derivatives (US Pat. Nos. 3,180,729, 4,278,746, JP-A-55-88064, 55-88065, 49-105537, 55-).
51086, 56-80051, 56-88141, 57-45545
No. 54-112637, No. 55-74546, etc.), a phenylenediamine derivative (US Pat. No. 3,615,404).
No. 51, Japanese Patent Publication No. 51-10105, No. 46-3712, No. 47-25336,
JP-A-54-53435, JP-A-54-110536, JP-A-54-119925, etc.), arylamine derivatives (US Pat.
7,450, 3,180,703, 3,240,597, 3,658,520
No. 4,232,103, 4,175,961, 4,012,376, JP-B-49-35702, 39-27577, JP-A-55-144250,
56-223437, West German Patent 1,110,518, etc.), amino-substituted chalcone derivative (US Patent 3,526,50)
No. 1), oxazole derivatives (U.S. Pat. No. 3,257,203, etc.), styrylanthracene derivatives (such as those described in JP-A-56-46234), fluorenone derivatives (JP-A-54-110837). And the like), hydrazone derivatives (US Pat. No. 3,717,462, JP-A-54-59143, JP-A-55-52063, JP-A-55-52064, and JP-A-55-467).
No. 60, No. 55-8495, No. 57-148749, JP-A-3-136059
Nos. 3-138654, etc.), stilbene derivatives (JP-A-61-210363, 61-228451, 61-14642).
Issue 61-72255, Issue 62-47646, Issue 62-36674, Issue 62
-10652, 62-30255, 60-934454, 60-94462
No. 60, No. 60-174749, No. 60-175052, No. 63-149652,
Japanese Patent Laid-Open No. 1-173034, 1-200262, etc.),
Porphyrin compound (JP-A-63-295695, JP-A-2-127)
95, etc.), aromatic tertiary amine compounds and styrylamine compounds (US Pat. No. 4,127,412, JP-A-53-27033, JP-A-54-58445, JP-A-54-149634, JP-A-54-64).
No. 299, No. 55-79450, No. 55-144250, No. 56-119132
Nos. 61-295558, 61-98353, 63-295695, JP-A 1-274154, 1-243393, 3-111485, etc.), butadiene compounds (JP-A 3-111484, etc.), polystyrene derivatives (JP-A-3-95291)
, Etc.) and hydrazone derivatives (Japanese Patent Laid-Open No. 3-13
No. 7187), triphenylmethane derivative, tetraphenylbenzidine derivative (JP-A-3-54289).
No. etc.) can be used,
Particularly preferred are porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds.

The structural formulas of specific exemplified compounds used for the p layer are shown below, but the present invention is not limited thereto.

[0043]

[Chemical 6]

Specific examples of the electron injecting compound having an electron transporting ability used for the n layer 6 include nitro-substituted fluorenone-derived thiopyrandioxide derivatives and diphenoquinone derivatives ("Polymer Preprints, Japan, vo1.37, No3, No.
P681, (1988) ", JP-A-3-152184, etc.), perylene tetracarboxyl derivative (" Jpn. Jour.
nalof Applied Physics, vol.27, No2, L269 (1988), `` Bul
1. Chem. Soc. Jpn., Vol. 25, L411 (1952) "), anthraquinodimethane derivative (JP-A-57-149259).
No. 58, No. 58-55450, No. 61-225151, No. 61-133750, No.
63-104061, etc.), fluorenylidene methane derivative (JP-A-60-69657, JP-A-61-143764, JP-A-61-143764)
148159, etc.), anthrone derivatives (such as those described in JP-A-61-225151 and 61-233750), oxadiazole derivatives (such as those described in JP-A-3-79692), Compounds such as a perinone derivative (described in JP-A-2-289676) and a quinoline complex derivative can be used.

The structural formulas of the specific exemplified compounds used for the n layer are shown below, but the present invention is not limited thereto.

[0046]

[Chemical 7]

[0047]

EXAMPLES Examples will be described below, but the present invention is not limited thereto.

Example 1 ITO Glass P110-HS (surface resistance 12Ω /
□ or less) it was UV10 ₃ washed with an in-propyl alcohol / water = 1/1 solution ultrasonic cleaning was repeated 10 times Toshiba Lighting & Technology Corporation batch processing type optical reformer.

On this substrate, the substrate temperature was set to a desired temperature under a vacuum of 6.0 × 10 ^-6 torr, and the p layer (80 nm) and the n layer (63 nm) were vacuumed using a quartz crucible as shown in Chemical formula 7. Was vapor-deposited while maintaining the above condition, and further an alloy of Mg: Ag = 10: 1 (atomic ratio) was vapor-deposited while maintaining the vacuum to prepare each sample.

[0050]

[Chemical 8]

The results are shown in Table 1.

[0052]

[Table 1]

As is clear from the results shown in Table 1, the examples of the present invention are superior to the comparative examples.

Example 2 Each sample was prepared in the same manner as in Example 1 except that the compounds of p layer and n layer were changed.

[0055]

[Chemical 9]

The results are shown in Table 2.

[0057]

[Table 2]

As is clear from the results in Table 2, the examples of the present invention are superior to the comparative examples.

Example 3 Each sample was prepared in the same manner as in Example 1 except that the compounds of the p layer and the n layer were changed.

[0060]

[Chemical 10]

The results are shown in Table 3.

[0062]

[Table 3]

As is clear from the results shown in Table 3, the examples of the present invention are superior to the comparative examples.

The samples of Examples 1 to 3 were evaluated by the following evaluation methods.

Evaluation method: Under a vacuum of -10 ^-3 torr, ITO was used as an anode, and MgAg alloy was used as a cathode, V = 10 V was applied, and the emission luminance was measured with a Minolta LS110 luminance meter over time.

The aggregation / crystallization was evaluated by observation with a polarization microscope.

○: No aggregation ×: Aggregation

[0068]

According to the organic thin film electroluminescent element and the method for producing the same of the present invention, the aggregation and crystallization of the organic layer can be controlled, and the effects of high brightness and high durability can be obtained.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a procedure for producing an organic thin film electroluminescent element.

FIG. 2 is a cross-sectional view showing a layer structure of an organic thin film electroluminescence element.

[Explanation of symbols]

 1 Substrate 2 Anode 3 Cathode 4 Light Emitting Layer 5 p Layer 6 n Layer 7 Organic Laminated Body S Inactive Substance T Transparent Top Plate

Claims (3)

[Claims] 1. An organic thin film electroluminescent device comprising a transparent substrate having at least an electrode and an upper electrode provided thereon by a vacuum vapor deposition method, and the substrate temperature during the production is in the range of -10 ° C to -196 ° C. An organic thin film electroluminescent element characterized by being formed by the method of 1. and its manufacturing method. 2. In the organic thin film electroluminescent device, at least a layer containing an organic compound represented by the following general formula [I] and a layer containing a styryl compound represented by the following general formula [II] are at least provided. An organic thin film electroluminescent element characterized by being provided with at least one layer. [Chemical 1] [In the formulas (Z1) to (Z4) of the residue Z of the general formula [I], R ₁
To R ₁₁ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted five groups described below; an alkyl group, a monovalent group derived from an unsaturated chain hydrocarbon, a heterocyclic group, and an aryl group. A group containing two or more nitrogen atoms, or a styryl group,
Anisyl group, amino group, alkylamino group, dialkylamino group, alkoxy group, alkoxycarbonyl group, aminocarbonyl group, aryloxycarbonyl group, carboxyl group, acyl group, aryloxyl group, aralkyl group, acylamino group, acyloxyl group, Represents a hydroxyl group, a cyano group, a nitro group, a sulfo group, a sulfonium group,
R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₆ and R ₇ , R ₇ and R ₈ , R ₈ and R ₉ , R ₉ and R ₁₀ , R ₁₀ and R ₁₁ are bonded to each other. And may form a substituted or unsubstituted saturated or unsaturated ring structure. X in the above formula (Z5) represents a substituted or unsubstituted heterocycle. ] [Chemical 2] [In the general formula [II], R ₁₂ and R ₁₃ are each independently a hydrogen atom, a substituted or unsubstituted four groups described below; an alkyl group, a heterocyclic group, an aryl group, an unsaturated chain hydrocarbon. R ₁₂ and R ₁₃ may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring structure. R ₁₄ is the following three substituted or unsubstituted groups; an alkyl group, an aryl group, an alkoxy group or-{p (C ₆ H ₄ )}-CH = C {(-R ₁₂ ) (-R ₁₃ )} Represents
R ₁₂ and R ₁₃ are as defined above. R ₁₅ is a hydrogen atom,
Substituted or non-substituted, the following three groups; an alkyl group, an aryl group, and an alkoxy group. ] 3. The organic compound represented by the general formula [I] is used as a light emitting substance, and the styryl compound represented by the general formula [II] is used as a hole transporting substance.
2. The organic thin film electroluminescent device according to.