CN1807396A - Anthracene derivative, organic electroluminescent device, and display device - Google Patents
Anthracene derivative, organic electroluminescent device, and display device Download PDFInfo
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Abstract
Disclosed is anthracene derivative with general formula (1), wherein X denotes substituted or unsubstituted C6-28 arylidene, substituted or unsubstitutedC5-21 bivalent heterocyclic radical; A and B respectively denote substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C6-28 aryl, substituted or unsubstituted C5-21 heterocyclic radical, and can be combined into a ring; Y<1> and Y<2> respectively denote hydrogen atom, substituted or unsubstituted C1-20 alkyl or C1-20 alkoxy; Z denotes substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C5-21 heterocyclic radical, hydrogen atom, substituted or unsubstituted C1-20 alkyl or C1-20 alkoxy.
Description
The cross reference of related application
The present invention comprises the theme of the JP 2005-013517 that submits to Japanese Patent office in the Japanese patent application JP 2005-009981 that relates on January 18th, 2005 and submit to Japanese Patent office and on January 21st, 2005, and its full content is hereby incorporated by.
Technical field
The present invention relates to be suitable for use as the organic materials that is used for organic electroluminescence device anthracene derivant, use the organic electroluminescence device of this anthracene derivant and comprise the display unit of this organic electroluminescence device.
Background technology
Recently, as consume low power and have the self-emission flat-panel monitor at the high speed of response and wide visual angle, the display unit that includes organic electroluminescence devices (being organic EL device) catches on.
Organic electroluminescence device comprises the organic layer that is clipped between negative electrode and the anode, and this organic layer is included in impressed current and has luminous electroluminescent organic material down.As organic layer, for example, develop wherein hole transmission layer, the luminescent layer that contains the organic electroluminescent material and electron transfer layer with the structure of this arranged in order on anode, or wherein luminescent material has been introduced electron transfer layer has the luminescent layer of electronic transmission performance with formation structure.
Using organic electroluminescence device to make under the situation of display unit, one of most important task is to guarantee the longer life and the reliability of electroluminescent organic material.In this case, the organic materials that constitutes organic electroluminescence devices is studied.
At first,, studied many derivatives, for example contained the anthracene derivant and the dianthracene derivative of amino or aryl and contain the anthracene derivant of styryl for material with anthracene skeleton.For example, with reference to Japanese Unexamined Patent Application open Nos.2003-146951,9-268284,9-268283,2004-67528 and 2001-284050 (patent document 1-5).
Specifically, need be to blue emitting material in the further improvement aspect purity of color, luminous efficiency and the luminescent lifetime.Up to now, for example carried out research based on Stilbene, styryl arylidene or anthracene derivant.For example, with reference to Material Science and Engineering:R:ReportsVolume 39, Issues 5-6, pp.143-222,2002 (non-patent document 1) and Applied PhysicsLetters (U.S.), Vol.67, No.26,1995, pp.3853-3855 (non-patent document 2).
Summary of the invention
But, need have higher luminous efficiency, the more long lifetime and the blue emitting material of high color purity more.
According to the embodiment of the present invention, the material that is suitable for use as the organic materials that constitutes organic electroluminescence devices is represented by general formula (1):
General formula (1)
X replacement or the unsubstituted divalent heterocyclic group representing to have the replacement or the unsubstituted arylidene of 6-28 carbon atom or have 5-21 carbon atom wherein; A and B represent to have the replacement or the unsubstituted alkyl of 1-20 carbon atom, the replacement with 6-28 carbon atom or unsubstituted aryl independently of one another or have the replacement or the unsubstituted heterocyclic group of 5-21 carbon atom, and A and B can be combined together to form ring; Y
1And Y
2Represent hydrogen atom independently of one another, have the replacement or the unsubstituted alkyl of 1-20 carbon atom or have the alkoxyl group of 1-20 carbon atom; The alkoxyl group of representing to have replacement or unsubstituted aryl, replacement or unsubstituted heterocyclic group, hydrogen atom, replacement or the unsubstituted alkyl of 6-30 carbon atom or having 1-20 carbon atom with Z with 1-20 carbon atom with 5-21 carbon atom.Here, alkyl comprises straight chain, side chain or cyclic alkyl.
According to another embodiment of the present invention, the material that is suitable for use as the organic materials that constitutes organic electroluminescence devices is represented by general formula (2):
General formula (2)
X wherein
1And X
2Expression independently of one another has the replacement or the unsubstituted arylidene of 6-28 carbon atom or has the replacement or the unsubstituted divalent heterocyclic group of 5-21 carbon atom; A, B, C and D represent to have the replacement or the unsubstituted alkyl of 1-20 carbon atom, the replacement with 6-28 carbon atom or unsubstituted aryl independently of one another or have the replacement or the unsubstituted heterocyclic group of 5-21 carbon atom, and A and B can be combined together to form ring and/or C and D and can be combined together to form ring; And Y
1And Y
2Represent hydrogen atom independently of one another, have the replacement or the unsubstituted alkyl of 1-20 carbon atom or have the alkoxyl group of 1-20 carbon atom.
Anthracene derivant by general formula (1) or (2) expression is used for the organic layer of organic electroluminescence device, and especially, is preferably used as blue emitting material.
Description of drawings
Fig. 1 is the schematic sectional view according to the organic electroluminescence device of embodiment of the present invention;
Fig. 2 is for being illustrated in the fluorescent absorption spectrographic figure of compound in the dioxane solution (17);
Fig. 3 is for being illustrated in the fluorescent absorption spectrographic figure of compound in the dioxane solution (45);
Fig. 4 is for being illustrated in the fluorescent absorption spectrographic figure of compound in the dioxane solution (46);
Fig. 5 is for being illustrated in the fluorescent absorption spectrographic figure of compound in the dioxane solution (49);
Fig. 6 is for being illustrated in the fluorescent absorption spectrographic figure of compound in the dioxane solution (60); And
Fig. 7 is for being illustrated in the fluorescent absorption spectrographic figure of compound in the dioxane solution (73).
Embodiment
Embodiments of the present invention are described below.
Anthracene derivant
The specific examples of the anthracene derivant of being represented by general formula (1) or (2) according to the present invention is described below.
General formula (1)
General formula (2)
In general formula (1) or (2), X, X
1And X
2Expression (a) independently of one another has the replacement or the unsubstituted arylidene of 6-28 carbon atom or (b) has the replacement or the unsubstituted divalent heterocyclic group of 5-21 carbon atom.
Wherein, the example of arylidene (a) comprises phenylene and derived from the divalent group of aromatic hydrocarbon, this aromatic hydrocarbon is biphenyl for example, terphenyl, naphthalene, anthracene, luxuriant and rich with fragrance, pyrene, fluorenes, fluoranthene, benzofluoranthrene, the dibenzo fluoranthene, the luxuriant and rich with fragrance alkene (acephenanthrylene) of vinegar, aceanthrylene, benzophenanthrene, vinegar naphtho-benzophenanthrene (acenaphthotriphenylene), _ perylene, benzo _, tetracene, seven days of the week alkene Pi, pentaphene, pentacene, tetraphenylene, trinaphthylene, benzophenanthrene, the dibenzo tetracene, benzanthrene, dibenzanthracene, the benzo tetracene, the naphtho-pyrene, benzopyrene, dibenzo pyrene, benzocyclooctene, anthracene tetracene (anthranaphthacene), with vinegar naphtho-fluoranthene.
In addition, arylidene (a) can be the divalent group derived from the arbitrary combination of these aromatic hydrocarbons.
Do not limit the position of substitution of arylidene (a) especially.In order to obtain to have the blue light than high color purity, preferably, the quantity of carbon atom that directly is attached to the aromatic hydrocarbon of nitrogen-atoms is 6-18, and more preferably, and the quantity of carbon atom that directly is attached to the aromatic hydrocarbon of nitrogen-atoms is 6-14.
The example of heterocyclic group (b) comprises derived from following divalent group: the arbitrary combination of thiophene, thionaphthene, oxazole, benzoxazole, oxadiazole, pyridine, pyrimidine, pyrazine, quinoline, benzoquinoline, dibenzoquinoline, isoquinoline 99.9, benzisoquinoline, quinazoline, quinoxaline, acridine, phenanthridines, azophenlyene, phenoxazine etc. and these compounds.
Do not limit the position of substitution of heterocyclic group (b) especially.In order to obtain to have the blue light than high color purity, preferably, the quantity of carbon atom that directly is attached to the heterocyclic group of nitrogen-atoms is 5-17, and more preferably, and the quantity of carbon atom that directly is attached to the heterocyclic group of nitrogen-atoms is 5-13.
In general formula (1) and (2), X, X
1And X
2Can be divalent group separately, wherein above illustrational arylidene (a) and heterocyclic group (b) are bonded to each other.
The substituent example of arylidene (a) or heterocyclic group (b) comprises halogen atom, hydroxyl, replacement or unsubstituted amino, replacement or unsubstituted alkyl, replacement or unsubstituted alkenyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocyclic radical, replacement or unsubstituted aralkyl, replacement or unsubstituted aryloxy, replacement or unsubstituted carbalkoxy and carboxyl.Do not limit the position of substitution of condensed ring especially and replace quantity.The example of halogen atom comprises fluorine, chlorine, bromine and iodine.
A, B, C and D in A in the general formula (1) and B and the general formula (2) represents that independently of one another (c) has replacement or unsubstituted heterocyclic group that the replacement of 1-20 carbon atom or unsubstituted alkyl, (d) have the replacement or the unsubstituted aryl of 6-28 carbon atom or (e) have 5-21 carbon atom.
Wherein, alkyl (c) can be straight chain, side chain or cyclic.The example of alkyl comprises methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, methylol, the 1-hydroxyethyl, the 2-hydroxyethyl, 2-hydroxyl isobutyl-, 1, the 2-dihydroxy ethyl, 1,3-dihydroxyl sec.-propyl, 2, the 3-dihydroxyl tertiary butyl, 1,2,3-trihydroxy-propyl group, chloromethyl, the 1-chloroethyl, the 2-chloroethyl, 2-chlorine isobutyl-, 1, the 2-Dichloroethyl, 1,3-two chloro isopropyls, 2, the 3-dichloro tertiary butyl, 1,2,3-three chloropropyls, brooethyl, the 1-bromotrifluoromethane, the 2-bromotrifluoromethane, 2-bromine isobutyl-, 1,2-two bromotrifluoromethanes, 1,3-dibromo sec.-propyl, 2, the 3-dibromo tertiary butyl, 1,2,3-three bromopropyls, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl-, 1,2-diiodo-ethyl, 1,3-diiodo-sec.-propyl, 2, the 3-diiodo-tertiary butyl, 1,2,3-triiodo propyl group, aminomethyl, the 1-amino-ethyl, the 2-amino-ethyl, 2-aminoisobutyric base, 1, the 2-diamino ethyl, 1,3-diamino sec.-propyl, 2, the 3-diamino tertiary butyl, 1,2,3-triamino propyl group, cyano methyl, the 1-cyano ethyl, the 2-cyano ethyl, 2-cyano group isobutyl-, 1,2-dicyano ethyl, 1,3-dicyano sec.-propyl, 2, the 3-dicyano tertiary butyl, 1,2,3-tricyano propyl group, the nitro methyl, the 1-nitro-ethyl, the 2-nitro-ethyl, 2-nitro isobutyl-, 1,2-dinitrobenzene ethyl, 1,3-dinitrobenzene sec.-propyl, 2, the 3-dinitrobenzene tertiary butyl, 1,2,3-trinitro-propyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, with the 4-methylcyclohexyl.
The example of aryl (d) comprises phenyl and derived from the monoradical of aromatic hydrocarbon, this aromatic hydrocarbon is biphenyl for example, terphenyl, naphthalene, anthracene, luxuriant and rich with fragrance, pyrene, fluorenes, fluoranthene, benzofluoranthrene, the dibenzo fluoranthene, the luxuriant and rich with fragrance alkene (acephenanthrylene) of vinegar, aceanthrylene, benzophenanthrene, vinegar naphtho-benzophenanthrene (acenaphthotriphenylene), _ perylene, benzo _, tetracene, seven days of the week alkene Pi, pentaphene, pentacene, tetraphenylene, trinaphthylene, benzophenanthrene, the dibenzo tetracene, benzanthrene, dibenzanthracene, the benzo tetracene, the naphtho-pyrene, benzopyrene, dibenzo pyrene, benzocyclooctene, the anthracene tetracene, with vinegar naphtho-fluoranthene.
In addition, aryl (d) can be the monoradical derived from the arbitrary combination of these aromatic hydrocarbons.
Do not limit the position of substitution of aryl (d) especially.In order to obtain to have the blue light than high color purity, preferably, the quantity of carbon atom that directly is attached to the aromatic hydrocarbon of nitrogen-atoms is 6-18, and more preferably, and the quantity of carbon atom that directly is attached to the aromatic hydrocarbon of nitrogen-atoms is 6-14.
The example of heterocyclic group (e) comprises derived from following monoradical: the arbitrary combination of thiophene, thionaphthene, oxazole, benzoxazole, oxadiazole, pyridine, pyrimidine, pyrazine, quinoline, benzoquinoline, dibenzoquinoline, isoquinoline 99.9, benzisoquinoline, quinazoline, quinoxaline, acridine, phenanthridines, azophenlyene, phenoxazine etc. and these compounds.
Do not limit the position of substitution of heterocyclic group (e) especially.In order to obtain to have the blue light than high color purity, preferably, the quantity of carbon atom that directly is attached to the heterocyclic group of nitrogen-atoms is 5-17, and more preferably, and the quantity of carbon atom that directly is attached to the heterocyclic group of nitrogen-atoms is 5-13.
In addition, A, B, C and D in A in the general formula (1) and B and the general formula (2) can be monoradical separately, and wherein aryl (d) and heterocyclic group (e) are bonded to each other.
The substituent example of aryl (d) or heterocyclic group (e) comprises halogen atom, hydroxyl, replacement or unsubstituted amino, replacement or unsubstituted alkyl, replacement or unsubstituted alkenyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted aromatic hydrocarbyl, replacement or unsubstituted aromatic heterocyclic radical, replacement or unsubstituted aralkyl, replacement or unsubstituted aryloxy, replacement or unsubstituted carbalkoxy and carboxyl.Do not limit the position of substitution of condensed ring especially and replace quantity.The example of halogen atom comprises fluorine, chlorine, bromine and iodine.
The large volume substituting group of appropriateness is introduced in any one of A in the general formula (1) and A, B, C and D in B and the general formula (2), this is at the crystallization control relevant with device property and to suppress bimolecular be effectively aspect exciting, and can further improve luminous efficiency and luminescent lifetime.Therefore, the substituting group that preferably will be selected from alkyl, alkoxyl group, alkenyl, heterocyclic radical and aryl is introduced in aryl (d) or the heterocyclic radical (e).
In addition, if A in the general formula (1) and B or A and B, and C and D combine by singly-bound, carbocyclic ring key etc. separately, compound has the second-order transition temperature and the excellent thermotolerance of improvement.
In addition, in general formula (1) and (2), Y
1And Y
2Expression (f) hydrogen atom, (g) has the replacement or the unsubstituted alkyl of 1-20 carbon atom or (h) has the alkoxyl group of 1-20 carbon atom independently of one another.
Wherein, alkyl is identical with alkyl (c) among above-mentioned A and the B.
Alkoxyl group (h) is represented by-OR, and the example of R comprises methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, methylol, the 1-hydroxyethyl, the 2-hydroxyethyl, 2-hydroxyl isobutyl-, 1, the 2-dihydroxy ethyl, 1,3-dihydroxyl sec.-propyl, 2, the 3-dihydroxyl tertiary butyl, 1,2,3-trihydroxy-propyl group, chloromethyl, the 1-chloroethyl, the 2-chloroethyl, 2-chlorine isobutyl-, 1, the 2-Dichloroethyl, 1,3-two chloro isopropyls, 2, the 3-dichloro tertiary butyl, 1,2,3-three chloropropyls, brooethyl, the 1-bromotrifluoromethane, the 2-bromotrifluoromethane, 2-bromine isobutyl-, 1,2-two bromotrifluoromethanes, 1,3-dibromo sec.-propyl, 2, the 3-dibromo tertiary butyl, 1,2,3-three bromopropyls, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl-, 1,2-diiodo-ethyl, 1,3-diiodo-sec.-propyl, 2, the 3-diiodo-tertiary butyl, 1,2,3-triiodo propyl group, aminomethyl, the 1-amino-ethyl, the 2-amino-ethyl, 2-aminoisobutyric base, 1, the 2-diamino ethyl, 1,3-diamino sec.-propyl, 2, the 3-diamino tertiary butyl, 1,2,3-triamino propyl group, cyano methyl, the 1-cyano ethyl, the 2-cyano ethyl, 2-cyano group isobutyl-, 1,2-dicyano ethyl, 1,3-dicyano sec.-propyl, 2, the 3-dicyano tertiary butyl, 1,2,3-tricyano propyl group, the nitro methyl, the 1-nitro-ethyl, the 2-nitro-ethyl, 2-nitro isobutyl-, 1,2-dinitrobenzene ethyl, 1,3-dinitrobenzene sec.-propyl, 2, the 3-dinitrobenzene tertiary butyl, with 1,2,3-trinitro-propyl group.
In general formula (1), Z represents that (i) has the replacement of 6-30 carbon atom or unsubstituted aryl, (j) and have the alkoxyl group that the replacement of 5-21 carbon atom or unsubstituted heterocyclic group, (k) hydrogen atom, (l) have the replacement or the unsubstituted alkyl of 1-20 carbon atom or (m) have 1-20 carbon atom.
Wherein, aryl (i) is identical with aryl (d) among above-mentioned A and the B, except amount of carbon atom is 6-30.Heterocyclic group (j) is identical with heterocyclic group (e) among above-mentioned A and the B.Alkyl (l) is identical with alkyl (c) among above-mentioned A and the B.Alkoxyl group (m) and above-mentioned Y
1And Y
2In alkoxyl group (h) identical.
Show the specific examples of compound (1)-(44) below as the anthracene derivant of representing by general formula (1).However, it should be understood that and the invention is not restricted to this.
Compound (1) compound (2)
Compound (4)
Compound (8)
Compound (44)
Show the specific examples of compound (45)-(96) below as the anthracene derivant of representing by general formula (2).However, it should be understood that and the invention is not restricted to this.
Compound (53) compound (54)
Compound (56)
Compound (57)
Compound (93) compound (94)
Compound (96)
Will be according to the present invention the anthracene derivant of any embodiment as the material of the organic layer that constitutes organic electroluminescence devices.Preferably, before being used for the manufacturing processed of organic electroluminescence device, increase the purity of anthracene derivant.This purity is preferably 95% or higher, and more preferably 99% or higher.In order to obtain to have this highly purified organic compound,, can use recrystallization, redeposition or use the post of silicon-dioxide or aluminum oxide to purify as the method for purification after anthropogenics.In addition, also can use known the purification to increase the method for purity by distillation.And, by repeating any these methods of purification or passing through with different method of purification combinations, can reduce the amount of the mixture in the luminous organic material of any embodiment according to the present invention, as unreacted matters, byproduct of reaction, catalyst residue or residual solvent, and therefore can obtain to have the more organic electroluminescence device of excellent specific property.
Organic electroluminescence device and comprise the display unit of this organic electroluminescence device
Describe organic electroluminescence device that uses above-mentioned anthracene derivant and the structure that comprises the display unit of this organic electroluminescence device in detail referring now to accompanying drawing.Fig. 1 is for schematically showing the organic electroluminescence device and the sectional view that comprises the display unit of this organic electroluminescence device according to embodiment of the present invention.
Display unit 1 shown in Figure 1 comprises substrate 2 and the organic electroluminescence device 3 that is configured in the substrate 2.Organic electroluminescence device 3 comprises with this sequential layer and is pressed in lower electrode 4, organic layer 5 and top electrode 6 in the substrate 2.From substrate 2 sides or from power on the utmost point 6 sides send light.Though Fig. 1 has showed the structure that wherein disposes the organic electroluminescence device 3 that is used for a pixel in substrate 2, display unit 1 has a plurality of pixels, and arranges a plurality of organic electroluminescence devices 3 for corresponding pixel.
The detailed structure of the independent assembly (promptly with this substrate 2, lower electrode 4 and top electrode 6 in proper order) that constitutes display unit 1 will be described below.
Substrate 2 is made by glass, silicon, plastic-substrates or the TFT substrate of wherein disposing thin film transistor (TFTs).Especially, when display unit 1 for wherein when substrate 2 sides are sent the optical transmission type, substrate 2 is made of the material with light transmission character.
The lower electrode 4 that is configured in the substrate 2 is used as male or female.In the drawings, show that wherein lower electrode 4 is that the anodic situation is as representative instance.
Make lower electrode 4 compositions become the shape of the drive system that is suitable for display unit 1.For example, when the drive system of display unit 1 was passive matrix, lower electrode 4 for example formed stripe shape.When the drive system of display unit 1 all provides the active array type of TFT for wherein giving each pixel, according to the independent pixel of arranging lower electrode 4 is carried out one patterned, and form lower electrode 4 in the insulating film of intermediate layer that covers TFTs so that it is connected with each TFT that each pixel is provided by the contact hole (not shown) that forms.
On the other hand, be configured in the top electrode 6 on the lower electrode 4 when between it, having organic layer 5, lower electrode 4 during for anode as negative electrode, and be used as anode during for negative electrode at lower electrode 4.In the drawings, showed that wherein top electrode 6 is the situation of negative electrode.
When display unit 1 is passive matrix, the stripe shape that top electrode 6 for example forms and the bar of lower electrode 4 intersects, and wherein these laminate portion that intersect each other corresponding to organic electroluminescence device 3.When display unit 1 was active array type, top electrode 6 formed covering the one side of substrate 2 with the shape of solid film, and top electrode 6 usefulness act on common (common) electrode of independent pixel.When the drive system of display unit 1 is active array type, in order to improve the open area ratio of organic electroluminescence device 3, the preferred top emission structure that adopts wherein the utmost point 6 sides from power on to send light.
As the anode material that constitutes lower electrode 4 (or top electrode 6), those with big as far as possible work function are desirable.Its preferred embodiment comprises nickel, silver, gold, platinum, palladium, selenium, rhodium, ruthenium, iridium, rhenium, tungsten, molybdenum, chromium, tantalum, niobium, these alloy and oxide compound, stannic oxide, tin indium oxide (ITO), zinc oxide and titanium oxide.
On the other hand, as the cathode material that constitutes top electrode 6 (or lower electrode 4), those with as far as possible little work function are desirable.Its preferred embodiment comprises magnesium, calcium, indium, lithium, aluminium, silver and these alloy.
For the electrode that sends the light that produces the organic electroluminescence device 3 from the one side, the material of suitably selecting to have light transmission character from above-mentioned materials is used for using.Especially, preferably use the material of transmission 30% or more light in organic electroluminescence device 3 wavelength of light emitted scopes.
For example, when display unit 1 for wherein when substrate 2 sides are sent the optical transmission type, the anode material with light transmission character for example ITO is used for as anodic lower electrode 4, and the cathode material (for example aluminium) with good reflection rate is used for the top electrode 6 as negative electrode.
On the other hand, when display unit 1 is when wherein the utmost point 6 sides are sent the top emission structure of light from power on, anode material (for example chromium or silver alloys) is used for as anodic lower electrode 4, and the cathode material (for example compound (MgAg) of magnesium and silver) with light transmission character is used for the top electrode 6 as negative electrode.Yet because MgAg has about 30% transmittance in green wavelength, preferred design organic layer 5 (it will be described below) makes optimizes the light intensity that resonator structure (resonator structure) is sent with increase.
Being clipped in organic layer 5 between lower electrode 4 and the top electrode 6 comprises with this sequential layer and is pressed in hole transmission layer 501, luminescent layer 503 and electron transfer layer 505 on the anode (lower electrode 4 in the drawings).
As hole transmission layer 501, form that can the single or multiple lift film or be used in combination known materials with mixture, NPB[N for example, N '-two (1-naphthyl)-N, N '-phenylbenzene (1,1 '-xenyl)-4,4 '-diamines], triphenylamine dipolymer, trimer or tetramer or starburst amine.
The luminescent layer 503 that is configured on the hole transmission layer 501 is features of the present invention and comprises the anthracene derivant of being represented by general formula (1) or (2) that it has compound (1)-(96 of mentioning as the example).The anthracene derivant of any embodiment has high hole transport character according to the present invention.Therefore, if use anthracene derivant separately or with 50 volume % or higher high density, if or use this anthracene derivant with mixture with other materials with hole transport character, observe light (it will be described below), cause the luminous efficiency in the luminescent layer 503 self to reduce from electron transfer layer 505.Therefore, in this case, preferably, between luminescent layer 503 and electron transfer layer 505, provide hole blocking layer.
More preferably, will be according to the present invention the anthracene derivant of any embodiment introduce in the luminescent layer 503 as object, and the anthracene derivant concentration in luminescent layer 503 expectation is 1 volume % or bigger and less than 50 volume %, preferred 1 volume %-20 volume %, and more preferably 1 volume %-10 volume %.
As mix the material of main part that uses with anthracene derivant, can use known materials ， such as oxadiazole, triazole, benzoglyoxaline, silole, styryl arylidene, to phenylene, spiral shell to phenylene or aryl anthracene derivant.
Electron transfer layer 505 for being configured on the luminescent layer 503 with this structure can use known materials, as Alq3, oxadiazole, triazole, benzoglyoxaline or silole derivative.
In addition, though do not illustrate in the drawings, hole injection layer can be inserted in as between anodic lower electrode 4 and the hole transmission layer 501.As hole injection layer, form that can the single or multiple lift film or be used in combination known materials, for example conductive polymers such as polyphenylene vinylene (PPV), copper phthalocyanine, starburst amine or triphenylamine dipolymer, trimer or tetramer with mixture.By inserting this hole injection layer, improve the hole injection efficiency, this is preferred.
In addition, though do not illustrate in the drawings, electron injecting layer can be inserted between electron transfer layer 505 and the negative electrode (top electrode) 6.Electron injecting layer can be made by alkalimetal oxide, alkaline metal fluoride cpd, alkaline earth metal oxide or alkaline-earth metal fluoride, for example Lithium Oxide 98min, lithium fluoride, cesium iodide or strontium fluoride.By inserting this electron injecting layer, improve electron injection efficiency, this is preferred.
Formation with organic layer 5 of the stepped construction that comprises above-mentioned materials can be used by the various organic materialss of currently known methods synthetic and use currently known methods such as vacuum moulding machine or spin coating to carry out.
Though do not illustrate in the drawings, for the display unit 1 that comprises organic electroluminescence device 3 with this structure, in order to prevent that organic electroluminescence device 3 from suffering the degradation (degrade) that is caused by the water in atmosphere, oxygen etc., be desirably in and form the sealing membrane of making by magnesium fluoride or silicon nitride (SiNx) in the substrate 2, to be coated with organic electroluminescence devices 3.Selectively, desirably, be coated with organic electroluminescence devices 3, and hollow parts purges or emptying with dry inert gas with sealed shell.
Though do not illustrate in the drawings, for the display unit 1 that comprises organic electroluminescence device 3 with this structure, can allow organic electroluminescence device 3 as the blue light emitting device, and red light-emitting device and green luminescence device provide every kind of pixel separately with the blue light emitting device, and these three kinds of pixels can be used as sub-pix (subpixel) to constitute a pixel.Each can be arranged in the substrate 2 to carry out panchromatic demonstration by a plurality of pixels that one group of three kinds of sub-pix constitutes.
The example that according to the present invention anthracene derivant of any embodiment is used for luminescent layer 503 has below been described wherein.But because the anthracene derivant of any embodiment has high hole transport character according to the present invention, anthracene derivant can be used as the material that constitutes hole transmission layer 501 or hole injection layer, and can be used as the dopant material that is used for these layers.
Embodiment
Describe below according to the synthetic embodiment 1 to 10 of the anthracene derivant of embodiment of the present invention and use the embodiment 1 to 34 of the organic electroluminescence device of this anthracene derivant according to embodiment of the present invention.
Synthesizing of synthetic embodiment 1 compound (2)
At first, with reference to synthesis type (1), by following method Synthetic 2,6-dibromoanthracene.
Synthesis type (1)
1) cupric bromide (11.8g) and nitrite tert-butyl (7.4g) are added in the 500ml acetonitrile, and under 50 ℃, stir.With 2,6-diamino-anthraquinone (5.7g) divides three parts to add in the reaction system, and stirs under 50 ℃ 8 hours.After reaction is finished, mixture is placed cool to room temperature, and under reduced pressure remove and desolvate by distillation.Water erase residual thing, and dry air two days is to produce 8.5g 2,6-dibromo-anthraquinone.
2) will generate 2,6-dibromo-anthraquinone (8.5g) is suspended in the 250ml methyl alcohol, and with ice-cooled following minute two portions to wherein adding sodium borohydride (3.5g).At room temperature after the stirred overnight, reaction soln is poured in the water (500ml), and filtered insolubles.Water cleans the solid that obtains, and dry air is to produce the 4.4g brown solid.
3) brown solid (4.4g) that generates is suspended in the 5N hydrochloric acid, and under 70 ℃, stirs 6 hours.After placing cooling, under reduced pressure filter insolubles, and water cleans the solid that obtains, and dry air is to produce the 7.8g green solid.
4) green solid (7.8g) that generates is suspended in the 250ml Virahol, and with ice-cooled following minute three parts to wherein adding sodium borohydride (8.4g).Subsequently, temperature is risen to 50 ℃ and stirred 8 hours.After placing cooling, reaction soln is poured in the water (500ml), and filtered insolubles.Water cleans the solid that obtains, and dry air is to produce green solid.
The green solid of cleaning generation with toluene is to produce 5.0g 2,6-dibromoanthracene.Its structure is confirmed by 1H-NMR, 13C-NMR and FD-MS.
With obtain like this 2,6-dibromoanthracene (3.0g), aromatic borate (A1) shown below are (3.0g), sodium hydroxide (0.5g) and four (triphenylphosphinyl) palladium (0.05g) add in the 100ml exsiccant dimethylbenzene (dryxylene), and make to be reflected in the nitrogen atmosphere and carried out under 100 ℃ 3 hours.
After reaction is finished, separate organic layer, water cleans twice and cleans once with saturated brine.Through after the anhydrous sodium sulfate drying, carry out vacuum concentration, purify by silica gel column chromatography subsequently, to produce the intermediate (1) of 1.6g yellow powder form.The intermediate (1) that generates is defined as target compound by mass spectroscopy (m/z 499).
Subsequently, with the intermediate (1) that generates (1.6g), aromatic borate (A2) shown below (0.8g), sodium hydroxide (0.2g) and four (triphenylphosphinyl) palladium (0.05g) add in the 100ml exsiccant dimethylbenzene, and make to be reflected in the nitrogen atmosphere and under 100 ℃, carried out 6 hours.
After reaction is finished, separate organic layer, water cleans twice and cleans once with saturated brine.Through after the anhydrous sodium sulfate drying, carry out vacuum concentration, purify by silica gel column chromatography subsequently, to produce the compound (2) of 1.1g yellow powder form.The compound (2) that generates is defined as target compound by mass spectroscopy (m/z 547).
Synthesizing of synthetic embodiment 2 compounds (5)
The same compound (5) that obtains the yellow powder form with synthetic embodiment 1 (2.5g), except replace aromatic borate (A2) with the aromatic borate (A3) shown in following.The compound (5) that generates is defined as target compound by mass spectroscopy (m/z 673).
Synthesizing of synthetic embodiment 3 compounds (17)
The same compound (17) that obtains the yellow powder form with synthetic embodiment 1 (2.5g), except replace aromatic borate (A2) with the aromatic borate (A4) shown in following.The compound (17) that generates is defined as target compound by mass spectroscopy (MS=573).Fig. 2 has showed the fluorescent absorption spectrum of the compound (17) that is generated in the Zai dioxane solution.
Synthesizing of synthetic embodiment 4 compounds (23)
Synthesizing of intermediate (2)
The same with the building-up process of intermediate in synthetic embodiment 1, the intermediate (2) that obtains the yellow powder form (2.0g), except with aromatic borate (A5) the replacement aromatic borate (A1) shown in following.The intermediate (2) that generates is defined as target compound by mass spectroscopy (m/z 447).
Subsequently, the same compound (23) that obtains the yellow powder form with synthetic embodiment 1 (1.7g), except replacing intermediate (1) with intermediate (2) and with aromatic borate (A4) the replacement aromatic borate (A2) shown in following.The compound (23) that generates is defined as target compound by mass spectroscopy (m/z 649).
Embodiment 1
Use the compound (2) that obtains among the synthetic embodiment 1, manufacturing transmission-type organic electroluminescence device as described below (with reference to figure 1).
The ito transparent electrode (anode) that forms thickness and be 190nm on substrate of glass 2 generating the ITO substrate, and carries out ultrasonic cleaning with neutral detergent, acetone and ethanol as lower electrode 4.Behind the ITO substrate drying, further carried out the UV/ ozonize 10 minutes.Subsequently, the ITO substrate is fixed on the substrate frame of depositing device (substrate holder), the pressure with the sediment chamber is decreased to 1.4 * 10 then
-4Pa.
At first, with the 0.2nm/ vaporator rate evaporation N shown below of second, N '-two (1-naphthyl)-N, N '-phenylbenzene [1,1 '-xenyl]-4,4 '-diamines (NPB) are to the thickness of 65nm, to form hole injection/transport layer 501 on the ITO transparent substrates.
Subsequently, use shown belowly 9,10-two (2-naphthyl) anthracene (ADN) as object, carries out the thickness of coevaporation to 35nm from isolating evaporation source with the total evaporation speed of about 0.2nm/ second as main body and compound shown below (2), to form luminescent layer 503, object concentration is 10 volume %.
Subsequently, evaporate the thickness of Alq3 to 18nm shown below with the vaporator rate of 0.2nm/ second, to form electron transfer layer 505.Evaporate the thickness of lithium fluoride (LiF) thereon, and in addition to 0.1nm, with the vaporator rate coevaporation magnesium of about 0.4nm/ second and silver to the thickness of 70nm (atomic ratio Mg: Ag=95: 5), to form negative electrode (top electrode 6).Thereby, make and wherein send radiative transmission-type organic electroluminescence device 3 from lower electrode 4.
When with 25mA/cm
2Current density generate with direct current driven organic electroluminescence device the time, driving voltage (a) is 5.9V, luminous efficiency is 6.1cd/A, and power efficiency is 2.1lm/W.In addition, be confirmed to be blue-light-emitting [luminosity (b)=1100cd/m
2, luminescence peak (c)=461nm].And, when with 1500cd/m
2Original intensity during with this electroluminescent device of constant current driven, the half-life (d) (that is elapsed time before the brightness of electroluminescent device is reduced to half of its initial value) is 1250 hours.
Embodiment 2 to 11
As embodiment 1, make transmission-type organic electroluminescence device 3, except in luminescent layer 503, using shown in the following table 1 compound (5) and other compounds replacement compound (2) as guest materials.Notice that the object concentration in each luminescent layer 503 is 10 volume %.
Table 1
| The luminescent layer guest materials | Driving voltage (a) (V) | Luminosity (b) (cd/m 2) | Glow color (c) | Half-life (d) (hour) | |
| Embodiment 1 | Compound (2) | 5.9 | 1,100 | Blue | 1,250 |
| Embodiment 2 | Compound (5) | 5.5 | 1,210 | Blue | 1,350 |
| Embodiment 3 | Compound (8) | 5.4 | 1,260 | Blue | 1,370 |
| Embodiment 4 | Compound (9) | 6.1 | 990 | Blue | 1,200 |
| Embodiment 5 | Compound (15) | 5.6 | 880 | Blue | 1,050 |
| Embodiment 6 | Compound (17) | 6.1 | 1,030 | Blue | 1,250 |
| Embodiment 7 | Compound (22) | 5.8 | 1,100 | Blue | 1,250 |
| Embodiment 8 | Compound (23) | 6.1 | 990 | Blue | 1,200 |
| Embodiment 9 | Compound (29) | 5.1 | 1,050 | Blue | 1,300 |
| Embodiment 10 | Compound (41) | 5.6 | 1,080 | Blue | 1,250 |
| Embodiment 11 | Compound (42) | 6.0 | 870 | Blue | 1,000 |
| Comparative example 1 | Compound (B1) | 5.9 | 1,050 | Green | 1,200 |
| Comparative example 2 | BCzVBi 5％ | 6.45 | 850 | Blue | 390 |
For the organic electroluminescence device of in embodiment 2 to 11, making as mentioned above, the measuring result (a) that as embodiment 1, obtains-(d) also be shown in Table 1.
Comparative example 1
As embodiment 1, make organic electroluminescence device,, use beyond the object that compound shown below (B1) replaces being made of the compound (2) as anthracene derivant with the object concentration of 10 volume % except in luminescent layer 503.
When with 25mA/cm
2Current density generate with direct current driven organic electroluminescence device the time, driving voltage (a) is 5.9V, luminous efficiency is 6.1cd/A, and power efficiency is 2.1lm/W.In addition, be confirmed to be green emitting [luminosity (b)=1050cd/m
2, luminescence peak (c): 485nm and 539nm], and do not obtain blue-light-emitting.And, when with 1500cd/m
2Original intensity during with this electroluminescent device of constant current driven, the half-life (d) (that is elapsed time before the brightness of electroluminescent device is reduced to half of its initial value) is 1200 hours.
Comparative example 2
As embodiment 1, make organic electroluminescence device, except in luminescent layer 503, beyond the object that the BCzVBi that uses description conduct in non-patent document 2 shown below to be used for the guest materials of blue-light-emitting replaces being made of the compound (2) as anthracene derivant.Setting object concentration is 5 volume %.
For the organic electroluminescence device of in comparative example 2, making like this, the measuring result (a) that as embodiment 1, obtains-(d) also be shown in Table 1.
It is evident that from table 1, use anthracene derivant [compound (2) etc.] according to embodiment of the present invention as the organic electroluminescence device among the embodiment 1 to 11 of luminescent material in, can obtain blue-light-emitting, in this anthracene derivant in the anthracene skeleton 9,10 are that replace for alkyl, the alkoxyl group replacement or unsubstituted.In addition, luminosity surpasses 800cd/m
2, and the half-life was above 1000 hours.
On the contrary, in using anthracene skeleton wherein 9,10 anthracene derivants that replace for aryl as the organic electroluminescence device in the comparative example 1 of luminescent material in, glow color is for green and do not obtain blue-light-emitting.Use BCzVBi as the organic electroluminescence device in the comparative example 2 of luminescent material in, though obtain blue-light-emitting, the half-life is short especially, is 390 hours.
As mentioned above, confirmed as the blue light emitting material in organic electroluminescence device, according to the present invention in the wherein anthracene skeleton of arbitrary embodiment 9,10 for alkyl replaces, alkoxyl group replaces or unsubstituted anthracene derivant is the material with excellent luminous efficiency and life characteristic.
Embodiment 12
In embodiment 12, make the top emission structure organic electroluminescence device.
On substrate of glass 2, be that to form thickness on the Ag alloy layer of 190nm be the ito transparent electrode (anode) of 11nm at thickness, as lower electrode 4, and carry out ultrasonic cleaning with neutral detergent, acetone and ethanol.After drying, further carried out the UV/ ozonize 10 minutes.Subsequently, substrate is fixed on the substrate frame of depositing device, the pressure with the sediment chamber is decreased to 1 * 10 then
-6Holder.
At first, on ito transparent electrode, evaporate the thickness of above-mentioned NPB to 24nm with the vaporator rate of 0.2nm/ second, to form hole injection/transport layer 501.Subsequently, use above-mentioned ADN as main body and compound (17) as object, carry out the thickness of coevaporation from isolating evaporation source with the total evaporation speed of about 0.2nm/ second to 35nm, to form luminescent layer 503, object concentration is 10 volume %.Subsequently, evaporate the thickness of above-mentioned Alq3 to 18nm with the vaporator rate of 0.2nm/ second, to form electron transfer layer 505.Evaporate the thickness of lithium fluoride (LiF) thereon, and in addition to 0.1nm, with the vaporator rate coevaporation magnesium of about 0.4nm/ second and silver to the thickness of 12nm (atomic ratio Mg: Ag=95: 5), to form negative electrode (top electrode 6).Thereby making wherein from power on, the utmost point 6 sends radiative top emission structure organic electroluminescence device 3.
When with 25mA/cm
2Current density generate with direct current driven organic electroluminescence device the time, driving voltage (a) is 4.6V, luminous efficiency is 2.0cd/A, and power efficiency is 2.1lm/W.In addition, be confirmed to be blue-light-emitting [luminosity (b)=787cd/m
2, luminescence peak (c)=461nm].The result, even confirmed by in using according to the wherein anthracene skeleton of embodiment of the present invention 9,10 for alkyl replaces, alkoxyl group replaces or the top emission structure organic electroluminescence device of unsubstituted anthracene derivant as luminescent material in, also can obtain blue-light-emitting.
Embodiment 13 to 17
As embodiment 1, make transmission-type organic electroluminescence device 3, except the object concentration that is made of the compound (2) as anthracene derivant is set at 1 volume %, 5 volume %, 10 volume %, 20 volume % and 40 volume % respectively in luminescent layer 503.
For the organic electroluminescence device of as above making, driving voltage (a), luminosity (b), glow color (c) and the half-life (d) of measuring as embodiment 1 are shown in the following table 2.
Table 2
| The concentration of luminescent layer compound (2) | Driving voltage (a) (V) | Luminosity (b) (cd/m 2) | Glow color (c) | Half-life (d) (hour) | |
| Embodiment 13 | 1％ | 6.6 | 700 | Blue | 830 |
| Embodiment 14 | 5％ | 6.4 | 930 | Blue | 1,100 |
| Embodiment 15 | 10％ | 5.9 | 1,100 | Blue | 1,250 |
| Embodiment 16 | 20％ | 5.5 | 900 | Blue | 1,030 |
| Embodiment 17 | 40％ | 5.2 | 790 | Blue | 870 |
It is evident that from table 2, is 1 volume % or bigger and less than 40 volume % by the concentration of setting anthracene derivant in the luminescent layer 503, for luminosity (b) and half-life (d), can keep high value.In addition, be preferably 1 volume %-20 volume % by setting concentration, and more preferably 1 volume %-10 volume %, luminosity (b) and half-life (d) can further be increased.
Synthesizing of synthetic embodiment 5 compounds (45)
At first, according to above-mentioned synthesis type (1) Synthetic 2,6-dibromoanthracene.
With generate 2,6-dibromoanthracene (3.0g), aromatic borate (A1) shown below are (5.8g), sodium hydroxide (1.5g), four (triphenylphosphinyl) palladium (2.0g) adds in the 200ml exsiccant dimethylbenzene, and allow be reflected at and carried out under 100 ℃ 6 hours.
After reaction is finished, filter the throw out that generates, water cleans, and cleans with the acetone suspension of heat, to produce the compound (45) of 2.8g yellow powder form.Confirm its structure by 1H-NMR, 13C-NMR and FD-MS.The compound (45) that generates is defined as target compound by FD-MS (m/z 664).The fluorescent absorption spectrum of the compound (45) that Fig. 3 is illustrated in the dioxane solution to be generated.
Synthesizing of synthetic embodiment 6 compounds (46)
The compound (46) that as synthetic embodiment 5, obtains the yellow powder form (2.5g), except replace aromatic borate (A1) by aromatic borate shown below (A6).Confirm its structure by 1H-NMR, 13C-NMR and FD-MS.The compound (46) that generates is defined as target compound by FD-MS (m/z 804).The fluorescent absorption spectrum of the compound (46) that Fig. 4 is illustrated in the dioxane solution to be generated.
Synthesizing of synthetic embodiment 7 compounds (49)
The compound (49) [2, two { 4-(N-(1-the naphthyl)-N-phenyl amino) phenyl } anthracenes of 6-] that as synthetic embodiment 5, obtains the yellow powder form (3.4g), except replace aromatic borate (A1) by aromatic borate shown below (A7).Confirm its structure by 1H-NMR, 13C-NMR and FD-MS.The compound (49) that generates is defined as target compound by FD-MS (m/z 764).The fluorescent absorption spectrum of the compound (49) that Fig. 5 is illustrated in the dioxane solution to be generated.
Synthesizing of synthetic embodiment 8 compounds (53)
The compound (53) [2,6-two { 3-(N, N-diphenyl amino) phenyl) phenyl } anthracene] that as synthetic embodiment 5, obtains the yellow powder form (2.5g), except replace aromatic borate (A1) by aromatic borate shown below (A8).Confirm its structure by 1H-NMR, 13C-NMR and FD-MS.The compound (53) that generates is defined as target compound by FD-MS (m/z 664).
Compound (53)
Synthesizing of synthetic embodiment 9 compounds (60)
The compound (60) that as synthetic embodiment 5, obtains the yellow powder form (2.5g), except replace aromatic borate (A1) by aromatic borate shown below (A9).Confirm its structure by 1H-NMR, 13C-NMR and FD-MS.The compound (60) that generates is defined as target compound by FD-MS (m/z 816).The fluorescent absorption spectrum of the compound (60) that Fig. 6 is illustrated in the dioxane solution to be generated.
Synthesizing of synthetic embodiment 10 compounds (73)
The compound (73) that as synthetic embodiment 5, obtains the yellow powder form (2.5g), except replace aromatic borate (A1) by aromatic borate shown below (A5).Confirm its structure by 1H-NMR, 13C-NMR and FD-MS.The compound (73) that generates is defined as target compound by FD-MS (m/z 816).The fluorescent absorption spectrum of the compound (73) that Fig. 7 is illustrated in the dioxane solution to be generated.
Embodiment 18
Use the compound (45) that obtains among the synthetic embodiment 5, as above-mentioned embodiment, make transmission-type organic electroluminescence device (with reference to figure 1).
When with 25mA/cm
2Current density generate with direct current driven organic electroluminescence device the time, driving voltage (a) is 5.7V, luminous efficiency is 6.4cd/A, and power efficiency is 3.5lm/W.In addition, be confirmed to be blue-light-emitting [luminosity (b)=1610cd/m
2, luminescence peak (c)=468nm].And, when with 1500cd/m
2Original intensity during with this electroluminescent device of constant current driven, the half-life (d) (that is elapsed time before the brightness of electroluminescent device is reduced to half of its initial value) is 1800 hours.
Embodiment 19 to 28
As embodiment 18, make transmission-type organic electroluminescence device 3,, use at the compound shown in the following table 3 (46) and other compounds to replace compound (45) in addition as guest materials except in luminescent layer 503.The object concentration of attention in each luminescent layer 503 is 10 volume %.
Table 3
| The luminescent layer guest materials | Driving voltage (a) (V) | Luminosity (b) (cd/m 2) | Glow color (c) | Half-life (d) (hour) | |
| Embodiment 18 | Compound (45) | 5.7 | 1,610 | Blue | 1,800 |
| Embodiment 19 | Compound (46) | 5.5 | 1,595 | Blue | 1,750 |
| Embodiment 20 | Compound (49) | 5.9 | 1,550 | Blue | 1,750 |
| Embodiment 21 | Compound (53) | 5.3 | 1,370 | Blue | 1,450 |
| Embodiment 22 | Compound (60) | 5.6 | 1.615 | Blue | 1,800 |
| Embodiment 23 | Compound (63) | 5.1 | 1,370 | Blue | 1,350 |
| Embodiment 24 | Compound (65) | 5.3 | 1,410 | Blue | 1,400 |
| Embodiment 25 | Compound (73) | 5.0 | 1,320 | Blue | 1,300 |
| Embodiment 26 | Compound (85) | 5.0 | 1,250 | Blue | 1,250 |
| Embodiment 27 | Compound (89) | 5.6 | 1,615 | Blue | 1,800 |
| Embodiment 28 | Compound (91) | 5.8 | 1,330 | Blue | 1,250 |
| Comparative example 3 | Compound (B2) | 5.9 | 1,520 | Green | 1,700 |
| Comparative example 4 | BCzVBi 5％ | 6.5 | 850 | Blue | 390 |
For the organic electroluminescence device of in embodiment 19 to 28, making as mentioned above, the measuring result (a) that as embodiment 18, obtains-(d) also be shown in Table 3.
Comparative example 3
As embodiment 18, make organic electroluminescence device,, use beyond the object that compound as follows (B2) replaces being made of the compound (45) as anthracene derivant with object concentration 10 volume % except in luminescent layer 503.
When with 25mA/cm
2Current density generate with direct current driven organic electroluminescence device the time, driving voltage (a) is 5.9V, luminous efficiency is 6.1cd/A, and power efficiency is 3.2lm/W.In addition, be confirmed to be green emitting [luminosity (b): 1520cd/m
2, luminescence peak (c): 482nm and 532nm], and do not obtain blue-light-emitting.And, when with 1500cd/m
2Original intensity during with this electroluminescent device of constant current driven, the half-life (d) (that is elapsed time before the brightness of electroluminescent device is reduced to half of its initial value) is 1700 hours.
Comparative example 4
As embodiment 18, make organic electroluminescence device, except the object that the BCzVBi that uses the conduct of describing as follows to be used for the guest materials of blue-light-emitting replaces being made of the compound (45) as anthracene derivant in non-patent document 2 in luminescent layer 503.Object concentration is set at 5 volume %.
For the organic electroluminescence device of in comparative example 4, making like this, the measuring result (a) that as embodiment 18, obtains-(d) also be shown in Table 3.
It is evident that from table 3, use anthracene derivant [compound (45) etc.] according to embodiment of the present invention as the organic electroluminescence device among the embodiment 18 to 28 of luminescent material in, can obtain blue-light-emitting, 9,10 in this anthracene derivant in the anthracene skeleton for alkyl replaces, alkoxyl group replacement or unsubstituted.In addition, luminosity surpasses 1000cd/m
2, and the half-life was above 1200 hours.
On the contrary, in using anthracene skeleton wherein 9,10 anthracene derivants that replace for aryl as the organic electroluminescence device in the comparative example 3 of luminescent material in, glow color is for green and do not obtain blue-light-emitting.Use BCzVBi as the organic electroluminescence device in the comparative example 4 of luminescent material in, though obtain blue-light-emitting, the half-life is short especially, is 390 hours.
As mentioned above, confirmed as the blue light emitting material in organic electroluminescence device, according to the present invention in the wherein anthracene skeleton of arbitrary embodiment 9,10 for alkyl replaces, alkoxyl group replaces or unsubstituted anthracene derivant is to have the excellent luminous efficiency and the material of life characteristic.
Embodiment 29
In embodiment 29, make the top emission structure organic electroluminescence device.
When with 25mA/cm
2Current density generate with direct current driven organic electroluminescence device the time, driving voltage (a) is 4.6V, luminous efficiency is 3.1cd/A, and power efficiency is 2.1lm/W.In addition, be confirmed to be blue-light-emitting [luminosity (b)=763cd/m
2, luminescence peak (c)=467nm].The result, even confirmed by in using according to the wherein anthracene skeleton of embodiment of the present invention 9,10 for alkyl replaces, alkoxyl group replaces or the top emission structure organic electroluminescence device of unsubstituted anthracene derivant as luminescent material in, also can obtain blue-light-emitting.
Embodiment 30 to 34
As embodiment 18, make transmission-type organic electroluminescence device 3, except the object concentration that is made of the compound (45) as anthracene derivant is set at 1 volume %, 5 volume %, 10 volume %, 20 volume % and 40 volume % respectively in luminescent layer 503.
For the organic electroluminescence device of as above making, driving voltage (a), luminosity (b), glow color (c) and the half-life (d) of measuring as embodiment 18 are shown in the following table 4.
Table 4
| Luminescent layer compound (45) concentration | Driving voltage (a) (V) | Luminosity (b) (cd/m 2) | Glow color (c) | Half-life (d) (hour) | |
| Embodiment 30 | 1％ | 5.8 | 1,140 | Blue | 1,270 |
| Embodiment 31 | 5％ | 5.5 | 1,520 | Blue | 1,710 |
| Embodiment 32 | 10％ | 5.7 | 1,610 | Blue | 1,800 |
| Embodiment 33 | 20％ | 5.1 | 1,080 | Blue | 1,650 |
| Embodiment 34 | 40％ | 4.8 | 850 | Blue | 1,300 |
It is evident that from table 4, is 1 volume % or bigger and less than 40 volume % by the concentration of setting anthracene derivant in the luminescent layer 503, for luminosity (b) and half-life (d), can keep high value.In addition, be preferably 1 volume %-20 volume % by setting concentration, and more preferably 1 volume %-10 volume %, luminosity (b) and half-life (d) can further be increased.
It will be understood by those of skill in the art that in the scope of claims or its Equivalent, depend on design requirements and other factors, can carry out various improvement, combination, recombinant and change.
Claims (13)
1. by the anthracene derivant of general formula (1) expression:
General formula (1)
X replacement or the unsubstituted divalent heterocyclic group representing to have the replacement or the unsubstituted arylidene of 6-28 carbon atom or have 5-21 carbon atom wherein;
A and B represent to have the replacement or the unsubstituted alkyl of 1-20 carbon atom, the replacement with 6-28 carbon atom or unsubstituted aryl independently of one another or have the replacement or the unsubstituted heterocyclic group of 5-21 carbon atom, and A and B can be combined together to form ring;
Y
1And Y
2Represent hydrogen atom independently of one another, have the replacement or the unsubstituted alkyl of 1-20 carbon atom or have the alkoxyl group of 1-20 carbon atom; And
The alkoxyl group that Z represents to have replacement or unsubstituted aryl, the replacement with 5-21 carbon atom or unsubstituted heterocyclic group, hydrogen atom, the replacement with 1-20 carbon atom or the unsubstituted alkyl of 6-30 carbon atom or has 1-20 carbon atom.
2. the anthracene derivant of claim 1, wherein in general formula (1), replacement or unsubstituted divalent heterocyclic group that X represents to have the replacement or the unsubstituted arylidene of 6-16 carbon atom or has 5-13 carbon atom;
A and B represent to have the replacement or the unsubstituted alkyl of 1-20 carbon atom, the replacement with 6-16 carbon atom or unsubstituted aryl independently of one another or have the replacement or the unsubstituted heterocyclic group of 5-17 carbon atom, and A and B can be combined together to form ring; And
Replacement or unsubstituted heterocyclic group that Z represents to have the replacement or the unsubstituted aryl of 6-30 carbon atom or has 5-21 carbon atom.
3. by the anthracene derivant of general formula (2) expression:
General formula (2)
X wherein
1And X
2Expression independently of one another has the replacement or the unsubstituted arylidene of 6-28 carbon atom or has the replacement or the unsubstituted divalent heterocyclic group of 5-21 carbon atom;
A, B, C and D represent to have the replacement or the unsubstituted alkyl of 1-20 carbon atom, the replacement with 6-28 carbon atom or unsubstituted aryl independently of one another or have the replacement or the unsubstituted heterocyclic group of 5-21 carbon atom, and A and B can be combined together to form ring and/or C and D and can be combined together to form ring; And
Y
1And Y
2Represent hydrogen atom independently of one another, have the replacement or the unsubstituted alkyl of 1-20 carbon atom or have the alkoxyl group of 1-20 carbon atom.
4. the anthracene derivant of claim 3, wherein in general formula (2), X
1And X
2Expression independently of one another has the replacement or the unsubstituted arylidene of 6-16 carbon atom or has the replacement or the unsubstituted divalent heterocyclic group of 5-13 carbon atom; And
A, B, C and D represent to have the replacement or the unsubstituted alkyl of 1-20 carbon atom, the replacement with 6-16 carbon atom or unsubstituted aryl independently of one another or have the replacement or the unsubstituted heterocyclic group of 5-17 carbon atom, and A and B, and C and D can be combined together to form ring separately.
5. claim 1 or 3 anthracene derivant, wherein in general formula (1) or (2), X, X
1And X
2Expression replaces or unsubstituted phenylene separately.
6. claim 1 or 3 anthracene derivant, wherein in general formula (1) or (2), Y
1And Y
2Represent hydrogen atom separately.
7. organic electroluminescence device comprises:
Pair of electrodes; And
Be clipped in the organic layer between this counter electrode, this organic layer comprises luminescent layer at least,
Wherein this organic layer comprises in the claim 1 to 6 each anthracene derivant.
8. the organic electroluminescence device of claim 7, wherein this anthracene derivant is as the material that constitutes this luminescent layer.
9. the organic electroluminescence device of claim 8, wherein this anthracene derivant is as blue light emitting material.
10. claim 8 or 9 organic electroluminescence device, wherein this luminescent layer comprises the anthracene derivant that content is no more than 20 volume %.
11. the organic electroluminescence device of claim 7, wherein in this organic layer, this anthracene derivant is as being selected from least a of hole-injecting material, hole mobile material and dopant material.
12. a display unit comprises:
Substrate; And
Be arranged in this suprabasil a plurality of organic electroluminescence devices, each organic electroluminescence device comprises the organic layer that is clipped between anode and the negative electrode, and this organic layer comprises luminescent layer at least,
Wherein this organic electroluminescence device comprises at least a claim 7 to 11 each organic electroluminescence device.
13. the display unit of claim 12, wherein in a plurality of pixels of part, the organic electroluminescence device that each is provided in the claim 7 to 11 is as the blue light emitting device.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP009981/05 | 2005-01-18 | ||
| JP2005009981A JP2006199595A (en) | 2005-01-18 | 2005-01-18 | Anthracene derivative, organic electroluminescent element and display |
| JP013517/05 | 2005-01-21 |
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| Publication Number | Publication Date |
|---|---|
| CN1807396A true CN1807396A (en) | 2006-07-26 |
| CN100417637C CN100417637C (en) | 2008-09-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB200610005028XA Expired - Fee Related CN100417637C (en) | 2005-01-18 | 2006-01-18 | Anthracene derivative, organic electroluminescent device, and display device |
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| JP (1) | JP2006199595A (en) |
| CN (1) | CN100417637C (en) |
Cited By (6)
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| CN101735107A (en) * | 2008-11-06 | 2010-06-16 | 索尼株式会社 | Aromatic amine compound, organic electroluminescent element including the same, and display device including organic electroluminescent element |
| CN102491881A (en) * | 2011-12-12 | 2012-06-13 | 南京信息工程大学 | Dibromo anthracene compound and preparation method and application thereof |
| CN103449947A (en) * | 2013-09-17 | 2013-12-18 | 烟台德润液晶材料有限公司 | Pre-purification method before sublimation and purification of OLED (organic light emitting diode) material |
| CN103855310A (en) * | 2012-11-30 | 2014-06-11 | 海洋王照明科技股份有限公司 | Organic electroluminescence device and preparation method thereof |
| US20150119582A1 (en) * | 2012-05-08 | 2015-04-30 | Carl Wagner | Naphthyl-containing compounds for light-emitting devices |
| CN107805494A (en) * | 2017-10-27 | 2018-03-16 | 广州工程技术职业学院 | One kind is by acetylene bridging fluorenes and anthracene derivant blue light material and preparation method |
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| JP2006282533A (en) * | 2005-03-31 | 2006-10-19 | Sony Corp | Bianthracene derivative, organic electroluminescent device, and display device |
| US20100133996A1 (en) * | 2007-05-09 | 2010-06-03 | Dongjin Semichem Co., Ltd | Novel anthracene typed compound and the organic electroluminescence display device using the same |
| JP4998228B2 (en) * | 2007-11-26 | 2012-08-15 | パナソニック株式会社 | Component verification system and component verification method |
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| JP7325731B2 (en) | 2018-08-23 | 2023-08-15 | 国立大学法人九州大学 | organic electroluminescence element |
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2005
- 2005-01-18 JP JP2005009981A patent/JP2006199595A/en active Pending
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2006
- 2006-01-18 CN CNB200610005028XA patent/CN100417637C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101735107A (en) * | 2008-11-06 | 2010-06-16 | 索尼株式会社 | Aromatic amine compound, organic electroluminescent element including the same, and display device including organic electroluminescent element |
| CN102491881A (en) * | 2011-12-12 | 2012-06-13 | 南京信息工程大学 | Dibromo anthracene compound and preparation method and application thereof |
| CN102491881B (en) * | 2011-12-12 | 2013-09-11 | 南京信息工程大学 | Dibromo anthracene compound and preparation method and application thereof |
| US20150119582A1 (en) * | 2012-05-08 | 2015-04-30 | Carl Wagner | Naphthyl-containing compounds for light-emitting devices |
| US9130172B2 (en) * | 2012-05-08 | 2015-09-08 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Naphthyl-containing compounds for light-emitting devices |
| CN103855310A (en) * | 2012-11-30 | 2014-06-11 | 海洋王照明科技股份有限公司 | Organic electroluminescence device and preparation method thereof |
| CN103449947A (en) * | 2013-09-17 | 2013-12-18 | 烟台德润液晶材料有限公司 | Pre-purification method before sublimation and purification of OLED (organic light emitting diode) material |
| CN107805494A (en) * | 2017-10-27 | 2018-03-16 | 广州工程技术职业学院 | One kind is by acetylene bridging fluorenes and anthracene derivant blue light material and preparation method |
| CN107805494B (en) * | 2017-10-27 | 2020-03-17 | 广州工程技术职业学院 | Acetylene-bridged fluorene and anthracene derivative blue light material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100417637C (en) | 2008-09-10 |
| JP2006199595A (en) | 2006-08-03 |
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