TW201121359A - Organic electroluminescence element - Google Patents

Abstract

An organic electroluminescence element is provided, which contains an organic layer between an anode and a cathode. The organic layer at least contains at least one luminescent layer, and a cathode-side adjacent layer that is adjacent to the cathode-side of the luminescent layer. The triplet state energy of the cathode-side adjacent layer is smaller than that of the luminescent material of the luminescent layer.

Description

[Technical Field] The present invention relates to an organic electroluminescence device (hereinafter sometimes referred to as "organic electroluminescence device", "organic E") L component"). [Prior Art] The organic electroluminescent element has the characteristics of spontaneous A, high-speed response, etc., and is expected to be applied to a flat panel display, etc., in particular, an organic thin film that transmits a hole is reported (a hole transport layer) A two-layer type (stacked type) organic electroluminescence device in which an organic thin film (electron transport layer) is laminated with an electron-transporting organic thin film, and the organic electroluminescence device is used as a low voltage of 1 〇V or less. The organic light-emitting element of the laminated type is mainly composed of a positive electrode/hole transport layer/light-emitting layer/electron transport layer/dippole, and the light-emitting layer is as in the case of the above-described j-type. The hole transport layer or the electron transport layer may also have the function. In order to achieve high luminous efficiency, such an organic light-emitting element has been scented as a host material of a phosphorescent material in the patent document 1 as a light-emitting and right---* mouth. A ripyrene) skeleton or anthracene skeleton of a condensed aromatic Fen 裱 compound. d. The proposed condensed aromatic ring compounds are all triplet energy side neighbors = will be = a small amount of small amount of the chemiluminescent layer of the cathode side of the luminescent layer::,: reveal no hint. The reason is that the 'anthracene of the light-emitting layer is also called an excitation suppression layer, and the side of the 201121359-JV/*. surface which is improved in luminous efficiency is preferably larger than the energy generated in the light-emitting layer (the cathode side is adjacent). The triplet energy of the layer is large (see Patent Document 2). Here, FIG. 1A is a view showing the relationship between the triplet energy of the light-emitting layer 6 and the cathode-side adjacent layer 7, and the triplet energy (τι) of the cathode-side adjacent layer 7 is smaller than the triplet energy of the light-emitting material of the light-emitting layer 6 (Τ1) Therefore, energy is easily moved from the light-emitting layer 6 to the cathode-side adjacent layer 7, and the light-emitting efficiency of the light-emitting layer 6 is lowered. On the other hand, in FIG. 1A, since the triplet energy (Τ1) of the light-emitting layer 6 is equal to or higher than the triplet energy (Τ1) of the cathode-side adjacent layer 7, the energy is not easily self-luminous. 6 Moving toward the cathode side adjacent layer 7, the luminous efficiency of the light-emitting layer 6 is improved. On the other hand, when the cathode-side adjacent layer having the doublet state in the triplet month b of the light-emitting material of the light-emitting layer is used, the light-emitting efficiency of the light-emitting layer can be improved, but the driving durability is deteriorated. Therefore, it is desired to provide an organic electroluminescence device which can improve the luminous efficiency at high luminance and high current density and improve the driving durability as soon as possible. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Publication No. 2009-196693 [Patent Document 2] Japanese Patent No. 3992929 SUMMARY OF THE INVENTION An object of the present invention is to provide a high brightness An organic electroluminescence device having improved luminous efficiency at high current density and improved driving durability. 201121359 Jozojpn is poor, and the above-mentioned problem has been repeated. The present inventors have made an effort to study the cathodes of the cathodes, which are adjacent to the cathode side of the light-emitting layer, and the electrons adjacent to the cathode side of the cathode-side adjacent layer. In the organic electroluminescent device of the organic layer, the triplet energy of the cathode side & dan θ is smaller than the triplet state of the luminescent material of the luminescent layer, which may be due to an increase in electron injectability and an illuminating layer. An organic electroluminescence device having high brightness and high current density for the next two years and excellent in driving durability can be obtained. θ The present invention is based on the above findings of the present inventors, and the method for solving the above problems is as follows. That is, an organic electroluminescence device characterized in that it has at least a layer of a light-emitting layer between the anode and the cathode, and a cathode-side adjacent layer adjacent to the cathode side of the light-emitting layer. In the organic layer, the triplet energy of the cathode side adjacent layer is smaller than the triplet energy of the light emitting material of the light emitting layer. The organic electroluminescence device according to the above-mentioned <1>, wherein the organic layer further includes an electron transport layer adjacent to a cathode side of the cathode side adjacent layer, and the triplet energy of the cathode side adjacent layer is smaller than the electron The triplet energy of the transport layer. The organic electroluminescence device according to the above-mentioned <1>, wherein the cathode-side adjacent layer contains a condensed aromatic ring compound. The organic electroluminescence device according to the above-mentioned <1>, wherein the 5 201121359 cathode-side adjacent layer contains a compound having an anthracene derivative skeleton represented by the following formula (II), and has the following At least one of the compounds of the anthracene derivative skeleton represented by the formula (I),

Rl R8

In the above formula (I), Ar1 and Ar2 are each independently a group derived from a substituted or unsubstituted aromatic ring having 6 to 20 carbon atoms. The above aromatic ring may be substituted with one or two or more substituents. The above substituent is an optionally substituted or unsubstituted aryl group having 6 to 5 fluorene, a substituted or unsubstituted alkyl group having 1 to 5 Å, a substituted or unsubstituted carbon number. a cycloalkyl group of 3 to 50, a substituted or unsubstituted alkoxy group having a carbon number of 丨~5 、, a substituted or unsubstituted aralkyl group having a core carbon number of 6 to 5 Å, substituted or not a substituted aryloxy group having a nuclear atom number of 5 to 5 Å, a substituted or unsubstituted arylthio group having 5 to 50 atomic number of the core, a substituted alkoxycarbonyl group having a reversed number of 1 to 50, Substituted or unsubstituted decyl, aryl, «atomic, cyano, and. When the aromatic ring is substituted by two or more substituted filaments, the above-mentioned filaments may be the same or different. The adjacent substituents may also be converted to each other to form an ortho-and-unsaturated ring structure of 201121359 iozwpu. R1 to R8 are an aryl group selected from a hydrogen atom, a substituted or unsubstituted nucleus having a carbon number of from 6 to 50, a substituted or unsubstituted heteroaryl group having a core number of 5 to 50, substituted or unsubstituted Alkyl having 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted a aryloxy group having a carbon number of 6 to 5 Å, a substituted or unsubstituted aryloxy group having a core number of 5 to 50, a substituted or unsubstituted arylthio group having a core number of 5 to 5 Å, A substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkylene group, a carboxyl group, a sulfonium atom, a cyano group, a nitro group, and a hydroxyl group. Further, adjacent substituents may be bonded to each other to form a saturated or unsaturated cyclic structure.

((L)m-ArIe)nb Formula (II) (IV), wherein the above formula (Π) towels '^ and # respectively represent an aromatic ring group having a core carbon number of 6 to 50 which is taken or not substituted. Substituting a substituted or unsubstituted phenylene group, a substituted or unsubstituted II group, a modified or unsubstituted substrate, or a substituted or non-extended smectite Dibenz〇sil〇lylene). An integer of 0 to 2, nb is an integer of 4, and $ is an integer of 〇~2. 201121359 \J*0 number 't is an integer of 〇~4. Further, L or Arla is bonded to any of the 1st to 5th positions of the oxime, and L or Ar2a is bonded to any of the 6th to the 10th positions of the oxime. Wherein, when nb + t is an even number, Arla, Ar2a, L satisfy the following (]) or (2) 〇 (1) Arla#Ar2a (where # represents a base of a different structure)

(2) Arla=Ar2W (2-1) m#s and / or nb#t, or (2-2) m=s and nb = t, (2-2-1) L or flower are respectively bonded to When the different bond torsion positions on Arla and Ar2a, or π (2-2-2) at the same bonding position where L or ytterbium is bonded to Arla and Ar2a, the substitution position of L or Arla&amp;Ar2a on 芘 is ! Bits with 6 bits, or 2 bits and 7 bits do not exist. The organic electroluminescence device according to the above <1>, wherein the cathode-side adjacent layer has a thickness of 1 nm to 1 〇 nm. [Effects of the Invention] As described above, according to the present invention, the prior problems can be solved, and it is possible to provide an energy-efficient electroluminescent element capable of achieving efficiency and driving durability. The above and other objects, features and advantages of the present invention will become more apparent. It will be described in detail with reference to the preferred embodiment of the present invention. [Embodiment] (Organic Electroluminescent Element) 8 201121359 The lx month organic electroluminescent device has a cathode side adjacent layer including at least a layer of light emitting layer and a cathode side adjacent to the cathode side of the light emitting layer between the anode and the cathode, and has an adjacent layer of the above-mentioned Yin Lake. The electron transport layer adjacent to the cathode side, and optionally other layers. The present invention is characterized in that the triplet energy of the cathode side adjacent layer is smaller than the triple energy of the light emitting material of the light emitting layer. If the triplet of the cathode side wiring layer is larger than the triplet state of the luminescent material of the light-emitting layer, although it is advantageous to prevent exciton diffusion, the electron affinity which is usually transmitted when electrons are transferred with a large triplet energy ( The energy level of electr〇n:ff y) is sometimes high, and sometimes it becomes the charge from the electron transport layer to the light-emitting layer (4). Furthermore, due to the main layer of the luminescent layer, the triplet energy of the material is greater than the tri-state energy of the luminescent material of the luminescent layer, so the relationship between the three energy of the __ layer and the ternary energy of the __ layer is as long as the triplet energy of the luminescent material of the optical layer It is enough to compare. Further, the triplet energy of the cathode side adjacent layer is preferably smaller than the triplet energy of the electron transport layer. If the triplet energy of the cathode side adjacent layer is greater than the triplet energy of the electron transport layer, when the excitons from the light emitting layer diffuse and fly over the contact layer, the excitons are sometimes in the electron transport layer. Consumption and efficiency decline. Therefore, the triplet energy of the cathode side adjacent layer in the cathode side adjacent layer, the light emitting material of the light emitting layer, and the electron transport layer becomes the smallest value. In the organic electroluminescent device, the luminescent material of the cathode-side adjacent layer and the triplet energy of the electron-transporting layer can use the oblique cutting technique in the state of the organic electroluminescent device. Organic Electric 201121359 After the oblique illumination of the illuminating element, the photo-luminescence (pL) method is used to estimate the triplet energy according to the difference of the mixed river spectra of the layers; or (2) by the flight time type II The surface analysis of the time of fight-Secondary Ion Mass Spectrometry (TOF'sms) is carried out by comparing the molecular formula and the method of determining the triplet energy from a single membrane. &lt;Light-emitting layer&gt; The material, shape, structure, size, and the like of the light-emitting layer are not particularly limited, and may be appropriately selected depending on the purpose. For example, the shape may be a film shape, a sheet shape, or the like, and The shape may be a square shape or a circular shape. The above structure may be a single layer structure or a laminated structure, and the above-described size may be appropriately selected depending on the use and the like. Regarding the material of the above-mentioned light-emitting layer, from the viewpoint of obtaining light emission from a triplet exciton (the light of the light), a phosphorescent light-emitting material and a host compound are suitable. Alternatively, the light-emitting layer may contain two or more phosphorescent materials to increase the color purity or to broaden the wavelength range of the light. - Phosphorescent material - The above-mentioned luminescent material is not particularly limited, and may be appropriately selected depending on the purpose. For example, a complex compound containing a transition metal atom or a lanthanoid atom may be mentioned. Examples of the transition metal atom include ruthenium, rhodium) (palladium) &gt;^|(tungstate)&gt;^(rhenium)^ iron, iridium, and the like. Among these, it is preferably chain, 201121359 JU^UJpil silver, the beginning, especially good for silver, the beginning. Examples of the above lanthanoid atom include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, and dysprosium. ), holmium, Erbium, thulium, ytterbium, lutecium, and the like. Among them, the best ones are 鈥, 铕, 釓. The ligand of the above complex compound is exemplified by G. Wilkinson et al.

Comprehensive Coordination Chemistry (released by Pergamon Press in 1987) and H.Yersin, "Photochemistry and Photophysics of Coordination Compounds j Springer-Verlag, Ltd., issued in 1987, Yamamoto Akira, "Organic Metal Chemistry_Basic and Application--" The ligands described in the house company's 1982 issue, etc. Specific ligands may include a halogen ligand (preferably a chlorine ligand), a Fangxiang stone anti-coordination group (for example, a cyclopentane anion (CyCl〇pentadjene anion), a benzene anion or a naphthyl anion). Etc., a nitrogen-containing heterocyclic ligand (eg, phenyl pyridine, benzoquinoline, quin〇Un〇1, bipyridyl, or morphine) (phenanthroiine), etc., a diketone ligand (eg, acetone acetate, etc.), a diacid ligand (eg, an acetate ligand, etc.), an alcoholate ligand (eg, a phenolate ligand, etc.), A carbon monoxide ligand, an isnitrile ligand, a cyano ligand, and the like. Among these, a nitrogen-containing heterocyclic ligand is particularly preferred. The above complex compound may contain a transition metal atom in the compound, and may be a polynuclear complex containing two or more transition metal atoms in addition to 201121359. It can also contain different kinds of metal atoms. Among these, examples of the phosphorescent material include, but are not limited to, the following compounds.

12

201121359 JOZDjpiI

13 201121359

The phosphorescent material to be used as the complex compound containing ruthenium is not particularly limited, and may be appropriately selected according to the purpose, and is preferably any one of the following general formula (2), general formula (3), and general formula (4). The compound represented.

General formula (2) 14 201121359 36263pit

General formula (3)

In the above formula (2), formula (3) and formula (4), η represents an integer of 1 to 3. Χ-Υ indicates a double tooth ligand. The ring Α represents a ring structure which may contain any one of a nitrogen atom, a sulfur atom and an oxygen atom. R11 represents a substituent, and ml represents an integer of 0 to 6. When ml is 2 or more, adjacent R11 may be bonded to each other to form a ring which may contain any one of a nitrogen atom, a sulfur atom and an oxygen atom, and the ring may be further substituted with a substituent. R12 represents a substituent, and m2 represents an integer of 0 to 4. When m2 is 2 or more, adjacent R12 may be bonded to each other to form a ring which may contain any one of a nitrogen atom, a sulfur atom and an oxygen atom, and the ring may be further substituted with a substituent. Further, R11 and R12 may be bonded to form a ring which may contain any one of a nitrogen atom, a sulfur atom and an oxygen atom, and the ring may be further substituted with a substituent. 15 201121359 The above ring A represents a ring structure which may contain any one of a nitrogen atom, a sulfur atom and an oxygen atom, and examples thereof include a 5-membered ring and a 6-membered ring. This ring may be substituted with a substituent. X-Y represents a bidentate ligand, and a monoanionic ligand of a double tooth or the like can be suitably cited. The monoanionic ligand of the above-mentioned double teeth may, for example, be a picolinate (pic), an acetylacetonate (acac) or a mono(meth)ethyl sulphide. (dipivaloylmethanate, third butyl aac) and the like. The ligand other than the above may be, for example, a ligand described in pages 89 to 91 of the Handbook No. 2002/15645 of Lamansky et al. The substituent of R11 and R12 is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include a halogen atom, an alkoxy group, an amine group, an alkyl group, a cycloalkyl group, and an aryl group which may contain a nitrogen atom or a sulfur atom. The aryloxy group containing a nitrogen atom or a sulfur atom may further be substituted. The groups adjacent to each other in the above R11 and R12 may be bonded to each other to form a ring which may contain a nitrogen atom, a sulfur atom or an oxygen atom, and a 5-membered ring or a 6-membered ring may be suitably used. This ring may be further substituted with a substituent. Specific examples of the specific compound represented by any one of the above formula (2), formula (3) and formula (4) include, but are not limited to, the following compounds. 16 201121359 36263pii'

17 201121359 36263pif (卜8)

(M2)

--ιο&gt;

Ϊ́-ΐ4)

&lt;Μ5)

(HID

18 201121359 36263ρΐί

(Η 7)

19 201121359 (1-24) (ίTM2β)

(1-25)

Other examples of the above phosphorescent material include the following compounds. 201121359

21 201121359 36263pif

DHO D-9

D-11

D-12 D-13 D -14

D-15 D-16

twenty two

201121359 JOZO^piI

The content of the above phosphorescent material is preferably 0.5 wt% to 30 wt%, more preferably 0.5 wt% to 20 wt%, and even more preferably 3 wt%, based on the weight of all the compounds forming the above-mentioned light-emitting layer. %~10 wt%. When the content is less than 0.5% by weight, the light-emitting efficiency may be small. When the content is more than 30% by weight, the light-emitting efficiency may be lowered due to the association of the phosphorescent material itself. - Host compound - As the host compound, a hole transporting host compound having excellent hole transport properties and an electron transporting host compound having excellent electron transport properties can be used. 23 201121359 - Hole-transporting host compound __ The above-mentioned hole-transporting host compound is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include pyrole, indole, and oxime. (carbazole), aza, π (azajnd〇ie), azacarbazole, pyrazol, imidaz〇le, poly aryl alkane, Pyrazoline, pyrazolone, phenylene diamine, arylamine, chalcone, styryl anthracene, fluorenone , hydraz〇ne, stilbene, siiazane, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidyne compounds, porphyrins a porphyrin compound, a polydecane compound, a poly(N-vinylcarbazole), an aniline copolymer, a thiene phene oligomer, a conductive polymer oligomer such as polythiophene, or an organic decane , carbon film or the compounds Biology. Among these compounds, preferred are an anthracene derivative, a carbazole derivative, an azaindole derivative, an azacarbazole derivative, an aromatic tertiary amine compound, and a porphin derivative, and more preferably have an intramolecular A compound having a skeleton, a taste skeleton, an azaindole skeleton, an azacarbazole skeleton, or an aromatic tertiary amine skeleton is particularly preferably a compound having a carbazole skeleton. Further, in the present invention, a host material in which a part or all of hydrogen of the above-mentioned host compound is substituted with ruthenium may be used (Japanese Patent Application No. 2008-126130, Japanese Patent Application No. 2〇〇4-5155〇6) Bulletin). 24 201121359 36263pit Specific examples of such a hole transporting host compound include, but are not limited to, the following compounds.

25

201121359 JOZOjpiI H-9

H-11

26 201121359 JO^C)3plt H-17 H_18

27 201121359 H-24 H-25

28 201121359 The content of the above-mentioned hole transporting host compound is preferably 10% by weight to 999 based on the weight of all the compounds forming the above-mentioned light emitting layer.

Wt% 'more preferably 20 wt% to 99.5 wt%' and further preferably 30 wt% to 99 wt% ° - electron transporting host compound - The above electron transporting host compound is not particularly limited and may be appropriately selected depending on the purpose. For example, it can be exemplified by a bite and a mouth. (), triazine, triazole, pyrazole, triazole, oxazole, oxadiazole, ketone, anthraquinone dimethane, anthrone (anthrone), diphenylquinone, thi〇pyran di〇xide, carbodiimide, methane, distyryl d, distryryipyrazine a fluorine-substituted aromatic compound, naphthalene perylene, or the like, a heterocyclic tetrahydrophenolic acid, a phthalocyanine, or a derivative of these compounds (which can form a condensed ring with other %). Metal complex of matter, metal phthalocyanine, various metal complexes represented by metal complexes containing benzoxazole and benzothiazole as ligands. Examples of the electron transporting host compound include a metal complex, an oxazol (benzimidazole derivative, an imidaz pyridine derivative, etc.), a azine derivative (pyridine derivative, pyrimidine derivative, triazine). Derivatives, etc.). Among them, in the present invention, a metal complex compound is preferred in terms of durability. More preferably, the above metal complex compound is a metal complex having a coordination group 29 201121359 base containing at least - money liver or oxygen atom or sulfur. The metal ion in the metal complex is not particularly limited, and is preferably cerium ion, magnesium ion, aluminum ion, gallium ion, zinc ion, indium ion, tin ion, platinum ion or palladium ion, more preferably cerium ion or aluminum. Ions, gallium ions, zinc ions, platinum ions or palladium ions, and thus preferably aluminum ions, zinc ions or palladium ions. Various known ligands are known for the ligand contained in the above metal complex, and examples thereof include "Photochemistry and ph〇t〇〇_ of Coordination Compounds" (Springer-Verlag, H=in '(4) issuance), "Organic Metal Scales and Applications" (=Huafanggong...Shanben County, served in the year). The above ligand is, for example, a nitrogen-containing heterocyclic ligand (preferably, carbon number: 〜30' is more preferably a carbon number of 2 to 20, particularly preferably a carbon number of 3 to 15, and the group may be 2 phases. Orbital wire. The contact is 2, the ligand. In addition, 2 phases, 6 teeth or less _ mixed ligand is also preferred. /, the position of the flat 其, the upper group, for example, may be mentioned as a noise coordination group (for example,吼Wei ς funeral ratio. Fixed ligand base, triplet ^ Wei group, etc.), warp group (for example, phenyl phenyl hydrazine _ simonyl, benzene ring ligand, transphenyl benzene ~ two good ;:=,) is particularly preferably · The number of slaves is 6~12, for example, 30

201121359 JO/OJpiI phenoxy, 1-naphthyloxy, 2·naphthyloxy, 2,4,6-trimethyl A=yl, etc.), heteroaryloxy ligand (preferably carbon number 1-3) ^更 = methoxy, oxy, methoxy 1 carbon number u ^), sulfur-burning ligand (preferably 吏 preferably for rabbits 1 to 20, particularly preferably carbon number 1 / Μ J sulfur Alkylthio group (preferably carbon t: 30, more preferably carbon number 6 to 2Q, county carbon number η), for example, =6 = group, etc.), heteroarylthio group coordination Base (compared to carbon number 3 ^ stone inverse number 1 to 20, particularly preferred carbon number 12, benzoquinone (tetra) base, 2 filaments, 2, 2-oxyl ligand (preferably carbon number) (4) + plug: f base f), burn, number 6 to 2 〇, for example, triphenyl group, ί number, etc.), aromatic _ sub-match: US stone inverse number 6 to 3. More preferably, the carbon number is 6 to 25 (8). The soil is a phenyl anion, a naphthyl group such as a heterocyclic anion ligand (preferably a carbon number Γ~; 0 =: a square fragrant group 25, particularly preferably a carbon number) 2~2〇 is better for the number of slaves 2~ Ions, (iv) anion, triammonium, ^yin::two::: from:, stupid, anion, two% = better ===== anionic ligand, etc. Bit group. Ionic ligand or aromatic heterocyclic anion with 31

201121359 ^OZOJpiI The above-mentioned metal complex electron transporting host compound can be exemplified by the Japanese patent, the eagle, the 216 Π 9 private report, the Japanese ruthenary 2 221 221 = the Japanese patent special open secret 4 Japanese Patent No. 2_-22 Picture No., Japanese Patent Laid-Open No. Specifically, such an electron transporting host compound may be, for example, a material 'but not limited to these materials. '

32 201121359

E-15 E-16

&gt;Pt

33 201121359 JOZOjpil E-17

E-21 E-22

The content of the above electron transporting host compound is preferably from 10 wt% to 99.9 yvt%, more preferably from 20 wt% to 99.5 wt%, even more preferably 30 wt%, based on the total weight of the compound forming the light-emitting layer. 99 wt% 〇 The above luminescent layer is a layer having a function of receiving a hole from an anode, a hole injection layer or a hole transport layer when an electric field is applied, and receiving electrons from a cathode, an electron injection layer or an electron transport layer to supply electricity Light is emitted by the recombination of holes and electrons. 34 201121359 成, (4) Gong (4) Method to form, transfer method, printing method ===, wet coating The thickness of the above-mentioned luminescent layer is suitable for formation. The choice is preferably 2 譲, and the TEL can be made according to (4), preferably φ, nm, and further == illuminating efficiency, more π, and 1 soil is nrn~200 nm. Further, the light-emitting layer may be a layer or two or more layers. For the above-mentioned &lt;cathode side adjacent layer&gt; j cathode contact layer, the light-emitting layer electrode (four) is connected to the organic θ ', and the hole that prevents transmission from the anode side to the light-emitting layer passes through the hole-blocking layer on the cathode side. Play the function. The triplet energy of the cathode side adjacent layer described above is smaller than the triplet energy of the luminescent material of the upper luminescent layer as described above. The cathode side adjacent layer preferably contains a condensed aromatic ring compound. The condensed aromatic ring compound is not particularly limited, and may be appropriately selected depending on the compound containing at least the derivative skeleton represented by the following formula (8) and at least the compound having the biological skeleton of the formula (1). One. 35 201121359 JOZOJpil

In the above formula (I), in the above formula (I), Ar1 and Ar2 are each independently a group derived from an aromatic ring having a core carbon number of 6 to 20 which is unsubstituted by the substitution f. In the above, the aromatic ring may be substituted with one or two or more substituents. The above substituent 疋 is selected from a substituted or unsubstituted aryl group having a core carbon number of 6 to 50, a substituted or undeuterated Weib% silk, a _ or an unsubstituted ring having a carbon number of 3 to 5 G. An alkoxy group having a carbon number, a substituted or unsubstituted carbon number, a substituted or unsubstituted aralkyl group having a core carbon number of 6 to 5 Å, a substituted or unsubstituted core atom number of 5 〜5G aryloxy, substituted or unsubstituted arylthio group having 5 to 5G of a nuclear atom, substituted by a substituted silk, 1 to 5G of a calamine group, substituted or unsubstituted Shi Xi A carboxyl group, a dentate atom, a cyano group, a base group, and a base group. When the above aromatic ring is substituted by two or more substituted filaments, the above substituents may be the same or different: adjacent substituents may be bonded to each other (tetra) and an unsaturated cyclic structure. R~R疋遂 from a hydrogen atom, a substituted or unaged aryl group having 6 to 50 aryl groups, a substituted or unsubstituted heterocyclic group having 5 to 5 fluorene groups, substituted or unsubstituted a carbon number such as a pyridyl group, a substituted substituted carbon group of 3 to 5 G, a substituted or unsubstituted carbon alkoxy group of 1 to 50, a substituted or unsubstituted carbon number of 6 ~5〇 of aralkyl 36 201121359

-JOZOjpiI group, substituted or unsubstituted aryloxy group having 5 to 50 atomic number, substituted or unsubstituted arylthio group having 5 to 50 nuclear atoms, substituted or unsubstituted slave number 1 ～50 of an alkoxy group, a substituted or unsubstituted alkyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group and a hydroxyl group. Further, the adjacent substituents may be bonded to each other to form a saturated or unsaturated cyclic structure.

(LVAr», Formula (II) wherein, in the above formula (II), Arla &amp; Ar2a respectively represent a substituted or unsubstituted aromatic ring group having a core number of 6 to 50. L is substituted or Unsubstituted phenyl, substituted or unsubstituted anthranyl, substituted or unsubstituted thiol or substituted or unsubstituted bismuth heterocyclopentadienyl. An integer of 〇~2, nb is an integer of 1 to 4's an integer of 0 to 2, and t is an integer of 〇~4. In addition, L or Arla is bonded to any of the i bits to 5 bits of 芘, B or Ar2a is bonded to any of 6 to 1 芘 of 芘. Wherein, when nb +1 is an even number, Arla, Ar2a, and L satisfy the following (1) or (2).

201121359 ^OZDjpiI (1) Arla#Ar2a (where # represents a base of a different structure) (2) Arla = Ar2a (2-1) m#s and / or nb#t, or (2-2) m=s And when nb = t, (2-2-1) L or 芘 are bonded to different bonding positions on Arla and Ar2a, respectively, (2-2-2) is the same as L or 芘 bonded to Arla&amp; Ar2a At the bonding position, the substitution position of L or Arla&amp; Ar2a on 芘 is 1 bit and 6 bits, or 2 bits and 7 bits are not present. Specific examples of the compound having the anthracene derivative skeleton represented by the following formula (II) are listed below, but the present invention is not limited to these compounds.

38 201121359

39 201121359 JQZQjpil Specific examples of the compound having the above-described 蒽 street biological skeleton represented by the general formula (I) are listed below, but the present invention is not limited to these compounds.

There is no particular limitation on the layer. The dry film forming method according to law, method, etc., the coating method, the transfer method, the printing method, and the thickness of the cathode side adjacent layer are preferably 1 nm to ^. . It is 2 nm to 5 nm. If the thickness is less than ι Μ better than the cathode side adjacent layer, the effect of high efficiency or high durability is not ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ The organic electroluminescent element is increased in voltage. High degree &lt;electron transport layer&gt; 201121359 mm The above electron transport layer is a layer having a function of accepting electrons from the cathode or cathode side and transmitting to the 11⁄4 pole side, and as described above, the triplet state of the above electron transport layer is preferably It is a triplet energy larger than the adjacent layer on the cathode side. The material of the above-mentioned electron transporting layer is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include 2,9-dimercapto•_4,7-phenylphenylene represented by the following structural formula. (bathocuproine), BCP), a material in which Li is doped in BCP, and tris(8-hydroxypyridinyl)aluminum (Alq) represented by the following structural formula, such as 8-hydroxyquinoline or a derivative thereof a group-based organometallic complex, BAlq (bis-(2-mercapto-8-hydroxyquinolin)-4-(phenylphenolated) aluminum (ΠΙ) represented by the following structural formula,

a quinoline derivative such as Bis-(2-methyl-8-quinolinolato)-4-(phenyl-phenolate)-alumini um(IIl)), a diterpene derivative, a triazole derivative, a morphine derivative, or a quinone Derivatives, pyridine derivatives, pyrimidine derivatives, quinoxaline derivatives, diphenyl hydrazine derivatives, nitro substituted funeral derivatives, and the like. Among these materials, a material in which Li is doped into BCP and BAlq are particularly preferable.

41 201121359

Alq

The electron transport layer may be, for example, an evaporation method, a wet film formation method, an electron beam method, a mineralization method, a reactive money plating method, a molecular beam epitaxy (MBE) method, or a cluster ion beam. (cluster i〇n beam) method, ion plating method, plasma polymerization method (high frequency excited ion plating method), molecular lamination method, Langmuir-Blodgett (LB) method A method such as a printing method or a transfer method is suitably formed. f The electronic transmission can be a single hybrid, or the organic electroluminescent device of the present invention is at the gate of the anode and the cathode and has at least at least _ layer of light, and between the secrets and the 丨^ 42 201121359 adjacent to the cathode side of the light-emitting layer, organic layer of the cathode side adjacent layer, electron transport layer adjacent to the cathode side, and example 2 of the thin adjacent layer: the system can be appropriately selected according to the purpose, the barrier layer, etc. .眺 层 layer, system of transport layer, electron-electron injection layer - the structure of the layer with the self-cathode or cathode side accepting electrons and the leaflet layer is formed by the &quot;&quot; species or two or more materials The thickness of the electroconductive layer formed of the multilayer of the composition or the different composition is not particularly limited, and may be from 2 nm to 200 nm, more preferably from 0.2 (10) to (10) nm, and even more preferably from 0.5 nm to 50 nm, depending on the purpose. The hole injection layer, the hole transport layer - / the above hole injection layer and the hole transport layer are layers having a function from the anode == to the cathode side. The hole injection layer and the electric power transmission θ may be a single layer structure or a (four) layer structure composed of the return. ^不Π种组成 The hole injection material or hole transport material used for the eight sons may be a low knife compound or a polymer compound. - (4) ΐί hole injection material or hole transmission material is not particularly limited, and can be selected privately according to (4) 'For example, transductive derivatives, flavors, three-sided biological H derivatives H derivatives, and rice derivatives 43 201121359 ^方基骏Charm, Btb (tetra) derivatives, (four) side derivatives, arylamine derivatives, amine-substituted axis derivatives, benzene = olefins, _ derivatives, hydrazine derivatives, stilbene-derived two =: biological, aromatic A tertiary amine compound, a phenethyl amidated diterpene sulphate methyl quinone compound, a phthalocyanine compound, a porphyrin-based r derivative, an organic Wei derivative, carbon, or the like. These materials may be used alone or in combination of two or more. In the hole injection layer and the hole transport layer, the dopant may contain an electron-accepting one, and the electron-containing dopant may have an organic substance as long as it is electron-accepting. Compounds and organic compounds can be used. The inorganic compound is not particularly limited, and may be, for example, a ferric chloride, a chlorinated chloride, a gallium chloride, a gas, or a gas, and the like. For example, there may be mentioned a compound having a time, a cyano group, a compound; an I-based compound, and an acid anhydride-based compound. The shaft compound can be used alone or in combination with the material == The amount of the dopant used is not particularly limited, and is based on Γ=Γη with respect to the hole transport layer material or the hole injection material, and further two Wt%~ 5° Wt% 'better is G.G5 Wt%~30 and then preferably 〇·1 wt%~30 wt%. 44 201121359 八4 The transmission layer is not particularly limited, and it can be formed by the wet coating method, the transfer method, and the printing method of the square wire material 'for example, 'Wei ^, Ju ^ ^ film making method'. The thickness of the above-mentioned hole injection layer and the hole transmission layer is better than that of the leg type: ~ is better than that of the above-mentioned hole and the other is - the electronic barrier layer - m The above-mentioned electronic barrier lion is prevented from the cathode to the The layer of luminescence ==:= is used as the above-mentioned material of the above-mentioned materials, and the above-mentioned electron blocking layer may be composed of the same group: or different species. The electron blocking layer is not particularly limited, and may be, for example, a vapor deposition method, a ruthenium plating method, a printing method, an inkjet method, etc., and the thickness of the layer is preferably lmn%. It is 1 nm~20() nm, more preferably I nm~50 nm, i隹; swi is inferior, and the horse is further preferably 3 nm~i〇nm. &lt;Electrode&gt; The cathode light-emitting element has at least one δ of the counter electrode, that is, the anode and the organic electroluminescence element, and preferably has an anode and a cathode. . Usually, the anode has only one. The electric/(10) electrode can be used as it is, and the cathode can be used as an electrode for injecting electrons into the organic layer as long as it has 45 201121359. Regarding the above electrode, its shape, structure, size, and the like can be appropriately selected depending on the organic electroluminescence device. The material of the electrode of the a* is, for example, a metal, a human metal oxide, a compound or a compound, or the like, and an anode. The material constituting the anode is exemplified by a recording, Conductive tin oxides such as sulphur, such as sulphur, sulphur, oxidized, oxidized steel, bismuth oxide, etc.; gold, silver, ruthenium, etc. a metal; a mixed or laminated product of the metal and the conductive metal oxide; an inorganic conductive material such as copper or copper sulfide; an organic conductive material such as polyaniline, polythiophene or polypyrrole, or the like ITf's laminates, etc. Among these materials, a conductive metal oxide is preferable, and ITO is particularly preferable in terms of productivity, high conductivity, transparency, and the like. _Cathode - Examples of the material constituting the cathode include alkali metal (for example, Li, Na, K, and C4), alkaline earth metal (for example, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloy, and lithium. Aluminum alloy, magnesium-silver alloy, rare earth metal such as indium or antimony. These materials may be used singly, and two or more types may be used in combination as long as they have both stability and electron injectability. Among these materials, in terms of electron injectability, alkali metal or alkaline earth metal is preferred, and in terms of excellent storage stability, it is particularly preferred to use 46 201121359 36263pif as a main material. The main body _ refers to the mixture of _, Ming and _ (for example, Zhong-Ming alloy, (4) alloy, etc.). The method of forming the metal is not particularly limited, and may be carried out according to a physical method such as a well-known method such as a gas ion (10) method, or a chemical method such as VV Vapor Deposltlon® CVD^cvd=. In these methods, the above-mentioned beauty can be formed by the method of selecting the material of the polar material. For example, when ΙΤ0 is selected as the material of the anode, it can be formed by a vapor deposition method, an ion surface method, or the like. When the genus # is used as the material of the cathode, it can be formed by legally selecting the gold and the like. Kind or two or more at the same time, or according to the other, Qingcheng can do _ _, use light lithography (____ borrowed or by _ laser, etc., C ask) and implement vacuum Luo plating or Qi It is carried out by a lift-off method or a printing method.曰 曰 & 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 基板 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机U "The material of the above-mentioned substrate of the middle layer of the caller is not particularly limited, and may be appropriately selected according to the purpose. 47 201121359 36263pit", for example, yttrium oxide stabilized yttrium oxide (YSZ), glass (alkali-free glass, soda lime glass (soda) Inorganic materials such as lime glass, etc.; polyesters such as polyethylene terephthalate, polybutylene P^thalate, polyethylene naphthalate, etc.; polystyrene, poly Carbonate, polyethersulfone (p〇lyether suif0ne), polyarene (p〇lyarylate), polyaniline, polycycloolefin, norbornene resin (n〇rb〇rneneresin), poly(gas trifluoroethylene), etc. The organic material, etc. The wire is not limited in terms of impurities, structure, or small size, and can be appropriately selected from the use and purpose of the organic electroluminescence element. Usually, the shape of the plate is preferably a plate shape. The structure may be a single-layer structure or a laminated structure, and a single layer of the substrate may be provided, and a moisture-proof layer (gas barrier layer) may be disposed on the surface or the back surface of the moisture-proof layer (gas barrier layer). The surname, 丨H, oxygen, etc. (10) 枓 枓 氮化 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 氮化 j j j j j j j j j j The material to be contained is not particularly limited as long as it is protected by a protection of 0. The substance which deteriorates the element is introduced into the element. The promotion of moisture or oxygen can be appropriately selected according to the purpose. In, Sn, Pb, 48 201121359

Metals of An, Cu, Ag, A, Ti, Ni, etc.; metal oxidation of Mg〇, Si〇, si〇2, A1203, GeO, NiO, CaO, BaO, Fe2〇3, y2〇3, Ti〇2, etc. Metal nitrides of SiNx, SiNxOy, etc.; metal fluorides of MgF2, LiF, AIF3, CaF2, etc.; polyethylene, polypropylene, polymethyl methacrylate, polyimine, polyurea, polytetrafluoroethylene, a copolymer of polychlorotrifluoroethylene, polydichlorodifluoroethylene, chlorotrifluoroethylene and dichlorodifluoroethylene, a copolymer obtained by copolymerizing a monomer mixture containing tetrafluoroethylene and at least one comonomer, A fluorinated copolymer having a cyclic structure in the main chain, a water-absorbent substance having a water absorption of 1% or more, a moisture-proof substance having a water absorption ratio of 〇1% or less, or the like. The method for forming the protective layer is not particularly limited, and may be appropriately selected according to the purpose. For example, a vacuum evaporation method, a sputtering method, a reactive sputtering method, a ΜΒΕ (molecular beam epitaxy) method, a cluster ion beam method, or the like may be mentioned. Ion electrowinning method, plasma polymerization method (high-frequency excitation ion plating method), electric CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method, and the like. - Sealed container - The organic electroluminescent element of the present invention can also be sealed with a sealed container using a sealed container. Further, a moisture absorbent or an inactive liquid may be enclosed in a space between the sealed container and the organic electroluminescence element. The water absorption (four) is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include cerium oxide, sodium oxide, oxidized clock, oxygen butterfly, sodium sulfate, sulfuric acid word, sulfuric acid lock, and antimony pentoxide (ph〇sph coffee). % coffee, chlorinated mother, magnesium gasification, vaporized copper, fluorinated, cesium fluoride, evolution, desert 49 201121359 36263pif $ hunger, molecular sieve (molecularsieve), zeolite (zeolite), magnesium oxide, the above inactive liquid There is no particular limitation, and it can be appropriately selected according to the purpose, for example, a paraffin type, a liquid stone _; all said to burn; I, a system, a gluten, a silicone oil, etc. _ Resin Sealing Layer - ::: The electroluminescent element is preferably sealed by sealing with a resin. (4) Elemental properties caused by oxygen scavenging from the atmosphere. The resin material of the resin sealing layer is not particularly limited. The selection may be, for example, an acrylic resin, an epoxy resin, a poly-wei resin, or a rubber-based resin = = a function of producing oxygen in the production * particularly preferably = tree month, and oxygen is preferably a heat hardening Type epoxy resin or photohardenable ring The production method is not particularly limited, and the method can be selected, for example, a method of coating a resin cell, a dry-sealing adhesive-incorporating function by steaming a coffee or the like, and the above-mentioned sealing adhesive has a moisture or oxygen-free self-end. For the above-mentioned sealing and bonding _ material used for the partial osmosis, the material cymbal material of the above-mentioned resin sealing layer 50 201121359 can be used. In this case, it is preferably an epoxy-based viscous &amp;= 枓, a hardening type point for preventing moisture penetration. The adhesive is preferably a photocurable adhesive or a heat, for example, a filler is added in the S, and a filler is added in the S. The filler (nitrogen cut) and the like are made of I. The viscosity is increased, plus: the adaptability of the material 'sealing adhesives enumeration = ^ sealing turn _ can contain dry. The above-mentioned money agent such as the amount =, oxidation name, etc.. The addition of the above desiccant is better _ wt = Ft agent, preferably 〇.01 Wt%~2〇wt%, sometimes the fruit is weaker. 'If the above addition amount exceeds 20 wt%, then the dry agent is evenly dispersed in the money bonding. 'Can be placed on the top, dry adhesive-free sealing adhesive by dispensing 11 (dispensel &quot;) The coating is applied in an amount, and after coating, the second substrate is superposed and cured to seal the film. Fig. 2 is a view showing an example of the layer configuration of the organic electroluminescence device of the present invention. An anode 2 (for example, an ITO electrode), a hole injection layer 3, a hole transport layer hopper, an electron blocking layer 5, a light-emitting layer 0, a cathode-side adjacent layer (hole blocking layer) 7, and an electron working on the glass substrate 1. The transmission layer 8, the electron injection layer 9, and the cathode 1 (for example, the A1_Li electrode) are formed by sequentially laminating layers. Further, the anode 2 (for example, an IT electrode) and the cathode 1 (for example, an A1_Li electrode) are via a power source. Connect to each other. 51 201121359 36263pit - Drive _ The organic electroluminescent device of the present invention can be applied with a direct current (and optionally an alternating component) voltage (usually 2 v (volts) to 15 V) or a direct current between the anode and the cathode. Light is obtained by current. The organic electroluminescent device of the present invention can be applied to an active matrix by a Thin Film Transistor (TFT). Amorphous, super-temperature polycrystalline, low-temperature polycrystalline, microcrystalline germanium, an oxide semiconductor, an organic semiconductor, a carbon nanotube, or the like can be applied as an active layer of a thin film transistor. The organic electroluminescence device of the present invention can be applied, for example, to a film transistor of the specification of WO2005/088726, the specification of Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei.曰 ° The organic electroluminescence device of the present invention is not particularly limited, and the light extraction efficiency can be improved by various known methods. For example, it can be processed by shape (for example, forming fine irregularities), control/board, layer, organic? The refractive index, which controls the thickness of the substrate, the IT layer, and the organic layer, improves the light extraction efficiency and improves the external quantum efficiency. Further, the silk type of the organic electroluminescence element from the present invention may be a top emission method or a bottom emission method. The organic electroluminescent device of the present invention may have a resonator structure. For example, a multilayer film mirror having a refractive index 四 (four) laminated film, a light-emitting transparent electrode, a light-emitting layer, and a light of a gold foil 52 201121359 may be superposed on a plate to be a reflector. In the meantime, it reflexes and resonates. In other preferred embodiments, in the transparent substrate, the poles function as reflectors, respectively, and the light reverberates between them to resonate. The rate produced in the generation, which will be effectively reflected by the two reflectors, is the value of the resonant wavelength. Calculation of the situation of the first aspect ίΐϊί 制平 9_ Delete 83 射射. In the second aspect, the dry form of the shape is the Japanese one. The organic electroluminescent element of the present invention is not particularly limited, and may be appropriately selected according to the purpose, and may be suitably used. For display components, displays (5) (4)), f (backlight), electronic photos, illumination sources, recording sources, exposure "sources, light sources, signs, billboards, interior trims (interi〇r), optical communications, etc.) A method of making the above-described organic electroluminescence display into a full-color type, as described in "Monthly Display" (September 2000), pages 33 to 37, is known as three primary colors (blue) A three-color luminescence method in which an organic electroluminescence device having light corresponding to color (B), chromatic (G), and red (R) is disposed on a substrate, and white luminescence of an organic electroluminescence device for white luminescence A white method of dividing into three primary colors by a color filter (c〇l〇rmter), and a blue light emission of an organic electroluminescence element for blue light emission 53 201121359 36263pif is converted into red (R) by a fluorescent pigment layer and Green (G) color conversion method . Further, a planar light source of a desired luminescent color can also be obtained by using a plurality of organic electroluminescent elements of different luminescent colors obtained by the above method in combination. For example, a white light-emitting source in which blue and yellow light-emitting elements are combined, and a white light-emitting source in which blue, green, and red light-emitting elements are combined may be mentioned. [Examples] Hereinafter, examples of the invention will be described, but the invention is not limited by the examples. (Example 1) - Preparation of an organic electroluminescence device - Indium Tin Oxide (ITO) was provided as an anode on a 0.5 mm thick, 2.5 cm square glass substrate by sputtering at a thickness of 1 〇〇 nm. ). Next, the IT crucible-attached glass substrate was placed in a cleaning vessel, ultrasonically cleaned in 2-propanol, and subjected to ultraviolet (Ultraviolet, UV)-ozone treatment for 3 () minutes. The following layers were steamed on the glass substrate with ruthenium by vacuum distillation. In addition, the vapor deposition rate in the following examples and comparative examples was 0.1 nm/s unless otherwise specified. The steaming speed is measured using a crystal oscillator (crystal 〇SClllat〇0. In addition, the thickness of each layer below is measured by a crystal vibrator. ^ First, on the anode (IT〇), the thickness becomes 12〇. The way of nm is formed by the vacuum method in the 4,4,4,3,3(Ν,Ν-(2-naphthyl)phenylamino)triphenylamine (2_τνατα) A hole injection layer of F4-TCNQ represented by the following structural formula is doped with 〇3 54 201121359 wt%.

NC,,CN

NC VIII CN F4-TCN0 Then, on the hole injection layer, NPD (N, N'_ represented by the following structural formula as a hole transport layer is formed by vacuum evaporation at a thickness of 7 nm. Dinaphthyl-N,N'-diphenyl-[1, fluorenyl-biphenyl]-4,4'-diamine). 55 201121359

JOZOJpiI

N P D is formed by the true *L on the hole-passing layer of the hole, and is expressed by the thickness of the formula 3. The upper: the key method is formed as an electronic resistive layer.

The core A was formed into a compound A of the following structural formula as a main charge by a vacuum distillation method so as to have a thickness of I01, and was 15 wt% with respect to the compound A. /. The light-emitting layer of Compound B represented by the following structural formula as a phosphorescent material. 56 201121359 36263pif

Compound B Then, a compound C (tbppy (1, 3, 6, 8-) represented by the following structural formula as a cathode-side adjacent layer was formed by vacuum evaporation on the light-emitting layer by a thickness of 3 nm. Tetrakis(4-biphenyl)芘)). 57 201121359

Then, on the cathode-side adjacent layer, bis-(2-mercapto-8-hydroxyquine) represented by the following structural formula as an electron transport layer was formed by a vacuum deposition method so as to have a thickness of 3 〇 nm. Boryl--4-(phenylphenolated)aluminum (111) (Bis-(2-methyl-8-quinolinolato)-4-(phenyl-phenolate)-alum inium (III), BAlq).

Lithium fluoride (LiF) as an electron injecting layer was formed by vacuum deposition on the electron transport layer by a vacuum deposition method. Then, a patterned mask (mask of the light-emitting area ^1 Γχ 2 mm) was placed on the electron 'master layer' to form a metal as a cathode by a vacuum deposition method to a thickness of 100. 58 201121359 36263pif The laminated body produced by the above operation is placed in an argon-substituted glove box, and a sealed can made of stainless steel and an ultraviolet curing type adhesive (XNR5516HV 'Nagase Ciba Limited Co., Ltd.) Made by the company) for sealing. By way of the above operation, an organic electroluminescent device of Example 制作 was fabricated. (Example 2) - Preparation of Organic Electroluminescence Element, Example 1, except that the compound C represented by the above structural formula was replaced with the compound D represented by the following structural formula as a cathode side adjacent layer, and examples 1 An organic electroluminescence device was produced in the same manner.

Compound D (Example 3) - Preparation of Organic Electroluminescence Element In Example 1, except that the compound (10) represented by the above structural formula was represented by the following structural formula (4, 4, _ double (2) An organic electroluminescent device was produced in the same manner as in Example 1, 201121359, except that the phenylene fluorene (DPVDPAN) was used as the ITO layer.

(Example 4) An organic electroluminescence device was produced in the same manner as in Example 1 except that the thickness of the cathode-side adjacent layer was changed from 3 nm to 10 nm. (Example 5) In the same manner as in Example 1, except that BAlq represented by the above structural formula was changed to a material in which 1 wt% of Li was incorporated in BCP represented by the following structural formula as an electron transport layer. An organic electroluminescent element is produced.

[Comparative Example 1] - Preparation of Organic Electroluminescence Device In the first example, an organic electroluminescence device was produced in the same manner as in Example 1 except that the cathode side adjacent layer was not provided. (Comparative Example 2) - Preparation of Organic Electroluminescent Element - In Example 1, except that the compound represented by the above structural formula was replaced with the compound F of the following structural formula * as the negative adjacent layer, Example 1 An organic electroluminescence device was produced in the same manner.

Compound F (Comparative Example 3) The same procedure as in Example 1 was carried out except that the cathode side adjacent layer was not provided and the BAlq exchange-organic electroluminescence device was produced in Example 1, except that π was changed to BCP + Li卩. Organic electroluminescent element. Then, the luminescent materials, the cathode-connecting layer, and the electron transporting layer of the produced solid m to the example 5 and the comparative example 1 to the comparative example 3 were measured as follows: 61 201121359 36263 pif The triplet state was measured. The results are not in Table 1. 〇&lt;Measurement of triplet energy&gt; The triplet energy is a spectrofluorometer F7000 manufactured by Hitachi, Ltd., and the luminescence lifetime is longer than that of fluorescence. The photoluminescence (PL) spectrum after excitation was obtained. [Table 1] Phosphorescent luminescent material cathode side adjacent electron ridge f transport layer species triplet energy species thickness (μιη) triplet energy species triplet energy comparison example 1 compound B 63 no BAlq 54 Comparative Example 2 Compound B 63 Compound F 3 ~~ 65 BAlq 54 Comparative Example 3 Compound B 63 No BCP + Li 58 Example 1 Compound B 63 Compound C 3 49 BAlq 54 Example 2 Compound B 63 Compound D 3 48 BAlq 54 Example 3 Compound B 63 Compound E 3 &lt;43 BAlq 54 Example 4 Compound B 63 Compound C 10 49 BAlq 54 Example 5 Compound B 63 Compound C 3 49 BCP + Li 58 Next, the produced Examples 1 to 5 and Comparative Examples 1 to 3 were measured as follows. Quantum efficiency, drive voltage, and drive durability (brightness half-life). The results are shown in Table 2. &lt;Measurement of external quantum efficiency&gt; A direct current having a current density of 25 mA/cm2 was applied to each element by using a power measuring unit 2400 (source measure unit 2400) manufactured by KEITHLEY Co., Ltd. to emit light. The luminance and luminescence spectrum were measured using a luminance meter SR-3 manufactured by T〇pc〇n. Based on these measurement results, the external quantum efficiency was calculated by the luminescence spectral conversion algorithm. &lt;Drive voltage&gt; 62

201121359 JOZOjpiI uses the power supply measuring unit Model 2400 manufactured by KEITHLEY to measure the driving voltage when the DC current is energized. &lt;Drive durability (brightness half-life)&gt; Driving durability was constant current driving at an initial luminance of 2,000 cd/m2, and the luminance half-life of Comparative Example and Comparative Example 3 was set to 100' at a relative value. The luminance half-life of the organic electroluminescent element using the same phosphorescent material in the light-emitting layer is shown. [Table 2]

As is apparent from the results of Tables 1 and 2, the example 丨 to the example 5 can achieve higher luminous efficiency and driving durability than the comparative examples j to the comparative example 3. Here, in Examples 1 to 5 and Comparative Examples 1 to 3, the compound B (phosphorescent luminescent material, triplet energy, 63 kcal/mol) represented by the upper = configuration was used in the light-emitting layer. When the compound G (phosphorescent green light-emitting material 'doublet energy: 58 kcal/m〇1) represented by the following structural formula is used in the light-emitting layer instead of the phosphorescent blue light-emitting material, the light-emitting material is used. Triplet energy of the cathode side adjacent layer and the electron transport layer 63 201121359

Jt&gt;2C) 3pit also becomes the same size relationship. Therefore, it has been shown that even when the compound G (phosphorescent green light-emitting material) represented by the structural formula is used, although the light-emitting wavelength of the light-emitting material is shorter in green and the triplet energy itself becomes smaller, the Pt complex is smaller. In the same way, the same effect can be obtained by the cathode side adjacent layer.

[Industrial Applicability] The organic electroluminescence device of the present invention can achieve high luminous efficiency and improved driving durability. Thus, for example, it can be suitably used for display elements, displays, backlights, electronic photographs, illumination sources, Recording wire, exposure light source/, reading light source, logo, billboard, interior trim, optical communication, etc. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the present invention, and those skilled in the art will be able to make some modifications and refinements within the scope and scope of the invention. The scope of the application is subject to the definition of the scope of the patent application. ‘, funeral [simple description of the map]

Fig. 1A is a view showing a relationship of triplet energy of a light-emitting layer and a cathode-side adjacent layer in a state of 64 201121359, showing a state in which the triplet energy of the adjacent layer on the cathode side is smaller than the triplet energy of the light-emitting material of the light-emitting layer. Fig. 1B is a view showing the relationship between the triplet energy of the light-emitting layer and the cathode-side adjacent layer, and shows a state in which the triplet energy of the light-emitting layer of the light-emitting layer is equal to or higher than the triplet energy of the cathode-side adjacent layer. Fig. 2 is a schematic view showing an example of a layer configuration of an organic electroluminescence device of the present invention. [Description of main component symbols] 1 : Substrate 2 : Anode 3 : Hole injection layer 4 : Hole transport layer 5 : Electron barrier layer 6 : Light-emitting layer 7 : Cathode side adjacent layer (hole blocking layer) 8 : Electron transport layer 9: Electron injection layer 10: Cathode Π: Organic electroluminescent element - T1: Triplet energy 65

Claims (1)

201121359 jozojpn VII. Patent application scope: 1. An organic electroluminescent device, characterized in that it has a cathode comprising at least a layer of light-emitting layer between the anode and the cathode, and a cathode adjacent to the cathode side of the light-emitting layer. The organic layer of the side adjacent layer, and the triplet energy of the cathode side adjacent layer is smaller than the triplet energy of the light emitting material of the light emitting layer. 2. The organic electroluminescent device according to claim 1, wherein the money layer further comprises an electron transport layer adjacent to a cathode side of the cathode contact layer, and the triplet energy of the cathode side adjacent layer is less than The triplet energy of the above electron transport layer. 3. The organic electroluminescence device according to claim 1, wherein the cathode side adjacent layer contains a condensed aromatic ring compound. 4. The organic electroluminescence device according to claim 1, wherein the cathode-side adjacent layer contains a compound having an anthracene derivative skeleton represented by the following formula (II), and has the following formula ( 1) at least one of the compounds of the anthracene derivative skeleton represented, Rl R8 In the above formula (I), Ari and Ar2 are each independently a group derived from an aromatic ring having an unsubstituted nucleocarbon number of 6 to 20, which is substituted by 66 201121359 -; The aromatic ring may be substituted with one or two or more substituents; the above substituent is an unsubstituted or unsubstituted aryl group having 6 to 5 fluorene, a substituted or unsubstituted carbon number of 1 〜5〇 of alkyl, substituted or unsubstituted cycloalkyl having 3 to 50 carbon atoms, substituted or unsubstituted carbon number 丨~Deng's alkoxy group, substituted or unsubstituted core carbon a 6- to 5-inch aralkyl group, a substituted or unsubstituted aryloxy group having 5 to 5 Å of a nuclear atom, a substituted or unsubstituted arylthio group having 5 to 50 atomic number, substituted Or an unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkylene group, a carboxyl group, a dentate atom, a cyano group, a nitro group and a hydroxyl group; or more than two or more aromatic rings When the substituent is substituted, the above substituents may be the same or different, and the adjacent substituents may be bonded to each other to form a saturated or unsaturated ring. Structure R; R8 is a hydrogen atom selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having a core number of 5 to 5 Å, substituted or Unsubstituted carbon number, alkyl group, substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or Unsubstituted arylalkyl group having 6 to 5 Å carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 carbon atoms, substituted or unsubstituted aryl group having 5 to 50 carbon atoms a thio group, a substituted or unsubstituted carbon alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkylene group, a carboxyl group, an il atom, a cyano group, a nitro group and a hydroxyl group; The substituents may also be bonded to each other to form a saturated or unsaturated cyclic structure; 67 201121359 Wherein A of the above-mentioned formula (8) in the formula (II) or unsubstituted core, respectively, represents that L is a sulphide-based sulphate ring group; a substituted naphthyl group, a stretched base , substituted or unsubstituted diphenyl fluorene extended base or substituted or not m is an integer of 〇 〜 2, 汕 is a number, t is an integer of 〇 ~ 4; , integer ' s is 〇 ~ 2 In addition, the L or Arla bond is in the W or W sleeve (four) position ~10:: = 1 2 3 4 5 bits of any one, L or (2) in 'when nb + t is even' Arla, Ar2a, L satisfy the following (1) 68 1 ArlaMr2a (here, green shows different structures of the base 2 into the broad: eight births 3 (2-1) m#s and / or nb / t, or (2-2) When m=s and nb = t, 4 (2-2-1) L or extension is respectively connected to Arla and eight different productions, or β 5 (2-2-2); L or ^ is bonded to When the same bonding position on Ar2a is used, the substitution position of L or Arla&amp;Ara on the 芘 is not in the position of ! and 6 or 2 and 7. 201121359 5. If the patent application is the first item The organic electroluminescence device, wherein the thickness of the cathode side adjacent layer 1 nm~10 nm. 69