CN102001908A - Asymmetric type tri-substituted anthracene and organic electroluminescent device containing same - Google Patents
Asymmetric type tri-substituted anthracene and organic electroluminescent device containing same Download PDFInfo
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Abstract
The invention relates to a novel 2-methylanthracene compound with a structure as shown in a formula (I) in the specification, and the novel 2-methylanthracene compound can be used for an organic electroluminescent device, wherein X represents a substituted or non-substituted aryl group composed of 6-20 carbon atoms, Y represents a substituted or non-substituted aryl group composed of 6-20 carbon atoms, and X and Y are not the same aryl group. The invention also relates to an organic electroluminescent device which is provided with an organic layer. The organic layer comprises the 2-methylanthracene compound with the structure as shown in the formula (I). The asymmetric type tri-substituted anthracene molecule of the invention has altitudinal asymmetry, and is used for obtaining smooth thin films with good heat stability so as to prolong the service life of the organic electroluminescent elements.
Description
Technical field
The present invention relates to a kind of asymmetric trisubstituted anthracene compounds.Because this kind anthracene compounds has good stability, one of application of this type of material is the host emitter as electromechanical excitation light dipolar body.The invention still further relates to the organic electroluminescent element and the OLED that use this kind anthracene compounds, wherein this OLED can be an indicating meter.
Background technology
(C.W.Tang after doctor Deng Qingyun of U.S. Kodak company delivers the OLED of low driving voltage, Applied Physics Letters, the 913rd page of the 51st volume, 1987), just cause that organic compound is applied in the research boom of OLED, OLED is to be interposed in (anode and negative electrode) between two electrodes, the sandwich structure of formation via organic medium (medium).Wherein, anode is the metal or the conductive compound of tool high work function, for example: tin indium oxide (ITO), indium-zinc oxide (IZO), stannic oxide (SnO
2), zinc oxide similar transparent metal oxides such as (ZnO), or can be membrane transistor (TFT) base material of polysilicon (poly-Si), non-crystalline silicon (a-Si) etc.; And negative electrode is the metal or the conductive compound of tool low work function, for example: gold (Au), aluminium (Al), indium (In), magnesium (Mg), calcium (Ca) or similar metal, alloy etc.; And have one in two electrodes at least for transparent or semitransparent, so that emission luminous energy penetrates efficiently; Organic medium can be formed by several layers according to the situation difference, wherein the thickness of each layer is not limited by strictness, usually at 5nm between 5 μ m, and representational between two electrodes, sandwiching three layers of molecule organic layer, these three layers comprise an electron transfer layer, a luminescent layer and an electric hole transport layer.
Be generally and reduce driving voltage and can add electric hole or electron injecting layer in addition, or improve luminous efficiency and increase electric hole or electronics barrier layer, and become four to six OLEDs that molecule organic layer is formed; Wherein electron injecting layer usually can be by alkali metal halide or basic metal inner complex nitrogenous, oxygen, for example: lithium fluoride, 8-quinolinolato lithium (Liq) etc.; And electric hole input horizon usually can be by metal benzene dimethylan (metalphthalocyanine) derivative, starlike polymeric amide (polyamine) derivative, polyaniline (polyaniline) derivative (Y.Yang et al, Syn.Met., 1997,87,171), perfluoro-compound, silicon-dioxide (SiO
2) (Z.B.Denget al, Appl.Phys.Lett., 1997,74,2227) or electric hole transport material doping oxide etc., for example: copper phthalocyanine (CuPc) (S.A.VanSlyke et al, Appl.Phys.Lett., 1996,69,2160), MTDATA (Y.Shirota et al, Appl.Phys.Lett., 1994,65,807), TPD
+SbCl
6 -(A.Yamamori et al, Appl.Phys.Lett., 1998,72,2147), PEDOT-PSS (A.Elschner et al, Syn.Met., 2000,111,139) etc.; Electron transfer layer can be by metallo-chelate (T.Sano et al nitrogenous, oxygen, J.Mater.Chem., 2000,10,157), sila cyclopentadiene (silole) derivative of oxadiazoles (oxadiazole) derivative, perfluorination multi-aromatic ring derivative, aromatic nucleus or heterocyclic substituted, oligo-thiophenes (oligothiophene) derivative or benzoglyoxaline (benzimidazole) derivative are formed, for example: three oxine aluminium (tris (8-quinolinolato) aluminum, Alq
3), polyhutadiene (PBD) (N.Johansson et al, Adv.Mater., 1998,10,1136), PyPySiPyPy (M.Uchida et al, Chem.Mater., 2001,13,2680), BMB-3T (T.Noda etal, Adv.Mater., 1999,11,283), PF-6P (Y.Sakamoto et al, J.Amer.Chem.Soc., 2000,122,1832), TPBI (Y.T.Tao et al, Appl.Phys.Lett., 2000,77,933) etc.; Electricity hole transport layer is generally the charge transfer material to electric hole that is used in the organic light-guide material and forms, this charge transfer material can be by triazole (triazole) derivative, oxadiazoles (oxadiazole) derivative, imidazoles (imidazole) derivative, phenylenediamine (phenylenediamine) derivative, starlike polyamines analog derivative, spiral shell shape structure (spiro-linked) molecule derivant or aromatic amine (arylamine) derivative are formed, for example: NPB or derivatives thereof (Y.Sato et al, Syn.Met., 2000,111,25), PTDATA (Y.Shirota et al, Syn.Met., 2000,111,387), spiro-mTTB (U.Bach et al, Adv.Mater., 2000,12,1060) etc.Because having the characteristic of low driving voltage and verified, OLED may be used on the full-color flat-panel screens, so the research of OLED and material has caused global attention and input.
In order to improve the glow color of OLED, luminous efficiency, stability of photoluminescence, component life and element production method etc., these improvement achievements can be consulted U.S. of having got permission the 4th, 356, No. 429, the 4th, 539, No. 507, the 4th, 720, No. 432, the 4th, 885, No. 211, the 5th, 151, No. 629, the 5th, 150, No. 006, the 5th, 141, No. 671, the 5th, 073, No. 446, the 5th, 061, No. 569, the 5th, 059, No. 862, the 5th, 059, No. 861, the 5th, 047, No. 687, the 4th, 950, No. 950, the 4th, 769, No. 292, the 5th, 104, No. 740, the 5th, 227, No. 252, the 5th, 256, No. 945, the 5th, 069, No. 975, the 5th, 122, No. 711, the 5th, 366, No. 811, the 5th, 126, No. 214, the 5th, 142, No. 343, the 5th, 389, No. 444, patent cases such as the 5th, 458, No. 977.
One of ultimate aim of OLED is to be applied on the flat-panel screens, and therefore, one can business-like element has more than and will have good luminous efficiency, glow color, and meeting business-like element also need have simultaneously good component life.
Aspect the blue light host emitter, the application of phenylanthracene derivative is reported in Japanese kokai publication hei 8-012600 communique, though anthracene derivant can be used to when the blue light host emitter, the life-span still must further improve.The application of another anthracene derivant is that the people such as Shi Jianmin of Kodak were in the United States Patent (USP) (U.S. the 5th in 1999,935, No. 721 patent cases) propose in 9,10 (2-naphthyl) anthracenes (ADN) are as the blue light host emitter in the organic light-emitting device, but ADN has easy crystalline phenomenon, and the life-span still also needs further improvement.Kodak disclosed the asymmetric anthracene derivant of the two phenylanthracenes of a 9-Nai Ji-10-in 2005 as the luminescent layer material of main part in WO042668.Disclose with the anthracene in No. 20070152565 patent case of the U.S. in 2007 is that axial two of skeleton replaces asymmetric compound as luminescent material.Disclose multiple anthracene derivant in TOHKEMY 2000-182776 communique, No. 2006154076 patent disclosure case of the U.S., No. 2006043858 patent disclosure case of the U.S. as electric hole transport material or luminescent layer material of main part, but, unactual synthetic actual its photoelectric characteristic of test of element of not making.Taiwan is announced in No. 593630 patent case and is disclosed symmetric 2 methyl-9,10 (2-naphthyl) anthracenes (MADN) as the blue light host emitter in the organic light-emitting device.
Summary of the invention
The inventor synthetic one has asymmetric three of novel structure and replaces anthracene derivative.In the derivative of No. 2 positions of anthracene, we find that via experiment the bromination of 2-methyl anthracene has high selectivity and high yield, can further synthesize to obtain asymmetric three replacement anthracene compounds, and be able to the highly purified organic electric-excitation luminescent material of volume production.Therefore the present invention's selection is a parent with 2-methyl anthracene compound, is described in more detail in the synthesis example.
The invention provides a kind of 2-methyl anthracene compound with novel formula (I):
Wherein, X is the aromatic yl group of 6 to 20 replacements that carbon atom is formed of aromatic base carbon number or non-replacement, and Y is the aromatic yl group of 6 to 20 replacements that carbon atom is formed of aromatic base carbon number or non-replacement, and X is not equal to Y.
The anthracene structural compounds of the three replacement asymmetrical type ad hoc structures that this formula (I) compound is represented, experiment finds to reduce driving voltage, improved thin film stability and promote the organic electroluminescent element life-span significantly, asymmetric three of this novel structure replaces anthracene derivative and can be applicable in the general organic electroluminescent element device, and anthracene compounds of the present invention can be used as the luminescent material of OLED.
The invention provides a kind of OLED, it comprises:
One substrate;
Two electrodes, wherein an electrode is arranged on this substrate; And
One organic layer, it is arranged between the described electrode, and comprise the have formula 2-methyl anthracene compound of structure of (I), wherein, X is the aromatic yl group of 6 to 20 replacements that carbon atom is formed of aromatic base carbon number or non-replacement, Y is the aromatic yl group of 6 to 20 replacements that carbon atom is formed of aromatic base carbon number or non-replacement, and X is not equal to Y.
Following is the part embodiment of preferable concrete 2-methyl anthracene compound material among the present invention:
Wherein, this organic layer includes an electric hole input horizon, an electric hole transport layer, an organic luminous layer, an electron transfer layer and an electron injecting layer in regular turn from nearly substrate to the direction away from substrate, and this 2-methyl anthracene compound with structure of formula (I) is contained in the wherein stratiform structure of this electricity hole input horizon, this electricity hole transport layer, this organic luminous layer, this electron transfer layer or this electron injecting layer.
Preferably, this 2-methyl anthracene compound with structure of formula (I) is contained in this organic luminous layer.
Preferably, the thickness of this organic layer is not more than 500nm.
Wherein, this OLED can be an indicating meter.
Wherein, this OLED can send redness, blueness, green, yellow or white light.
The present invention is by the organic layer in the OLED being mixed the have formula 2-methyl anthracene compound of structure of (I), can increase luminous efficient, and can with other compound, with as luminescent material red, blue, green, yellow, white light, so can be applied in the various OLEDs.
Description of drawings
Fig. 1 is the structural representation of general OLED;
Fig. 2 A, Fig. 2 B are respectively individual material and make the BIV figure of blue light element after luminous and with current density luminous efficiency is figure; Fig. 2 C is that individual material is made the luminous spectrogram of blue light element after luminous; Fig. 2 D makes ruddiness, green glow, dark blue, pale blue, the gold-tinted element luminous spectrogram after luminous for the B601 material;
Fig. 3 A, Fig. 3 B, Fig. 3 C are respectively ADN, without anneal, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope;
Fig. 4 A, Fig. 4 B, Fig. 4 C are respectively ADN and hold temperature after 1 hour, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope under atmosphere, 90 ℃;
Fig. 5 A, Fig. 5 B, Fig. 5 C are respectively MAND without anneal, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope;
Fig. 6 A, Fig. 6 B, Fig. 6 C are respectively MADN and hold temperature after 1 hour, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope under atmosphere, 90 ℃;
Fig. 7 A, Fig. 7 B, Fig. 7 C are respectively formula (II) compound without anneal, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope;
Fig. 8 A, Fig. 8 B, Fig. 8 C are respectively formula (II) compound and hold temperature after 1 hour, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope under atmosphere, 90 ℃;
Fig. 9 A, Fig. 9 B, Fig. 9 C are respectively formula (IV) compound without anneal, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope;
Figure 10 A, Figure 10 B, Figure 10 C are respectively formula (IV) compound and hold temperature after 1 hour, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope under atmosphere, 90 ℃;
Figure 11 A, Figure 11 B, Figure 11 C are respectively formula (VI) compound without anneal, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope;
Figure 12 A, Figure 12 B, Figure 12 C are respectively formula (VI) compound and hold temperature after 1 hour, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope under atmosphere, 90 ℃;
Figure 13 A, Figure 13 B, Figure 13 C are respectively formula (VII) compound without anneal, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope;
Figure 14 A, Figure 14 B, Figure 14 C are respectively formula (VII) compound and hold temperature after 1 hour, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope under atmosphere, 90 ℃.
Description of reference numerals: 10-OLED; The 11-substrate; The 12-anode layer; 13-electricity hole input horizon; 14-electricity hole transport layer; The 15-luminescent layer; The 16-electron transfer layer; The 17-electron injecting layer; The 18-cathode layer; The 19-power supply; The 20-organic layer.
Embodiment
Below in conjunction with accompanying drawing, be described in more detail with other technical characterictic and advantage the present invention is above-mentioned.
The present invention can be applicable in several different OLEDs, and wherein necessary composition comprises negative electrode, anode and be arranged at organic layer between this negative electrode and the anode, and this organic layer can comprise electric hole input horizon, electric hole transport layer, luminescent layer and electron transfer layer.
As shown in Figure 1 be most typical structure, wherein this OLED 10 comprises a substrate 11, one is arranged at the anode layer 12 on this substrate 11, one is arranged at the organic layer 20 on this anode layer 12, one is arranged at the power supply 19 that metallic cathode layer 18 on this organic layer 20 and two ends are connected to this anode layer 12 and cathode layer 18, this organic layer 20 comprises an electric hole input horizon 13 that is stacked by this anode layer 12 to cathode layer 18 directions, one electric hole transport layer 14, one luminescent layer 15, one electron transfer layer 16 and an electron injecting layer 17, when applying a voltage to anode layer 12 and cathode layer 18, the electronics that electric hole that anode layer 12 is produced and cathode layer 18 are produced can inject this organic layer 20 and then be combined into exciton (excitons), and just can the scattering bright dipping when exciton is reduced to ground state.
And these several layers employed material of following careful description.At first must be noted that in other forms, can be with the location swap of cathode layer and anode layer, so that cathode layer is arranged on the substrate, perhaps substrate can directly be treated as anode layer or cathode layer, moreover the total thickness of the organic layer that stacks with each layer preferably is equal to or less than 500nm.
It is noted that the person with usual knowledge in their respective areas can make organic electroluminescent element or device according to the compound that prior art described in existing skill or the specification sheets of the present invention or existing method utilize the present invention to ask.The suitable material of each component structure beyond the input horizon of electric hole in organic electroluminescent element of the present invention or the device below is described.
Substrate
Substrate can be a light transmission or opaque according to the direction that light radiated, if desire to make the emission energy of emission light (EL) to be observed by the substrate place, then substrate must have light peneration, in this case, generally all is to use glass or organic materials; And if EL emission to be desire see through top electrode observes, then whether the logical light of lower layer support thing will become unimportant, therefore can be that light penetrates, photoabsorption or luminous reflectance, at this moment, the material of substrate can use but not be restricted to glass, plastic cement, semiconductor material, pottery and circuit board material, and this kind component structure must provide the top electrode of light-permeable certainly.
Anode
Conductive anode layer is made on the substrate usually, and when EL radiation be when seeing through anode observation, then anode must be transparent or be transparent for some radiation substantially; Application can be general common transparent anode-indium tin oxide (indium tin oxide as anodic material of the present invention, ITO), but it is spendable that other metal oxides are still, include, but are not limited to the adulterated zinc oxide of aluminium or indium (indium doped zincoxide, IZO), magnesium-indium oxide (magnesium-indium oxide) and nickel-tungsten oxide (nickel-tungsten oxide), except these oxide compounds, metal nitride as gan (gallium nitride), as the metal selenide of zinc selenide (zinc selenide) with as the metallic sulfide of zinc sulphide (zinc sulfide), all can use as the anodic material.Radiation is to be observed through top electrode for EL, and this negative electrode is in the application of top electrode, the anodic light transmission recedes into the background, and can use any conductive material, the material of transparent, opaque or reflection all can, this uses down that spendable material includes, but are not limited to gold, iridium, molybdenum, palladium and platinum.General anode material, no matter whether transparent, its work content rate is usually more than or equal to 4.1eV, needed anode material deposits usually by rights, for example evaporation, sputter, chemical vapour deposition or electrochemical method etc., and anode can be with little shadow Exposure mode (photolithography) etched patternization of knowing.
Electricity hole transport layer (hole-transporting layer, HTL)
The electric hole transport layer of organic electroluminescent element comprises an electric hole conducting compound at least, for example fragrant tertiary amine, what inferred now is that this kind compound will contain the tervalent nitrogen-atoms of bond on carbon atom at least, and this carbon atom will have one to be a wherein element of aromatic nucleus at least; Wherein a kind of form of these aromatic series tertiary amines can be an arylamines, for example single aryl amine, two aryl amine, three aryl amine or high molecular aryl amine groups; The model of unit molecule type three aryl amine is described in the 3rd, 180, No. 730 patent cases of the U.S. by people such as Klupfel; And other three aryl amine that are fit to are to be exposed in the U.S. the 3rd by people such as Brantley, 567, No. 450 and the 3rd, 658, No. 520 patent cases are relevant for one or more vinyl free radicals and/or comprise the three aryl amine that at least one group that accommodates active hydrogen replaces.
The employed a kind of aromatic series tertiary amine of behaving most is by the U.S. the 4th, 720, No. 432 and the 5th, 061, No. 569 the patent case is described: the aromatic series tertiary amine that comprises at least two aromatic series tertiary amine groups, the illustration of below listing for useful aromatic series tertiary amine, it comprises but is not limited in 1, two (4-two-right-tolyl aminocarbonyl phenyl) hexanaphthenes of 1-, 1, two (4-two-right-tolyl the aminocarbonyl phenyl)-4-phenyl-cyclohexane-s of 1-, 4,4 '-two (phenylbenzene amido) four benzene, two (4-dimethyl amido-2-aminomethyl phenyl)-phenylmethanes, N, N, N-three (right-tolyl) amine, 4-(two-right-tolyl amido)-4 '-[4 (two-right-tolyl amido)-styryl] Stilbene, N, N, N ', N '-four-right-tolyl-4,4 '-benzidine, N, N, N ', N '-tetraphenyl-4,4 '-benzidine, N, N, N ', N '-four-1-naphthyl-4,4 '-benzidine, N, N, N ', N '-four-2-naphthyl-4,4 '-benzidine, the N-phenyl carbazole, 4,4 '-two [N-(1-naphthyl)-N-phenyl amido] biphenyl, 4,4 '-two [N-(1-naphthyl)-N-(2-naphthyl) amido] biphenyl, 4; 4 "-two [N-(1-naphthyl)-N-phenyl amido] are right-terphenyl, 4,4 '-two [N-(2-naphthyl)-N-phenyl amido] biphenyl, 1, two [N-(1-the naphthyl)-N-phenyl amido] naphthalenes of 5-, 4,4 '-two [N-(9-anthryl)-N-phenyl amido] biphenyl, 4; 4 "-two [N-(1-anthryl)-N-phenyl amido] are right-terphenyl, 4,4 '-two [N-(2-phenanthryl)-N-phenyl amido] biphenyl, 4,4 '-two [N-(8-fluorine anthrene base)-N-phenyl amido] biphenyl, 4,4 '-two [N-(2-pyrenyl)-N-phenyl amido] biphenyl, 4,4 '-two [N-(the thick tetraphenyl of 2-)-N-phenyl amido] biphenyl, 4,4 '-two [N-(2-perylene base)-N-phenyl amido] biphenyl, 4,4 '-two [N-(the severe base of 2-)-N-phenyl amido] biphenyl, 2, two (two-right-tolyl amido) naphthalenes of 6-, 2, two (two-(1-naphthyl) amidos) naphthalenes of 6-, 2, two [N-(1-naphthyl)-N-(2-naphthyl) amido] naphthalenes of 6-, N, N, N ', N '-four (2-naphthyl)-4; 4 "-two amidos-right-terphenyl, 4,4 '-two N-phenyl-N-[4-(1-naphthyl)-phenyl] and amido } biphenyl, 4,4 '-two [N-phenyl-N-(2-pyrenyl) amido] biphenyl, 2, the two [N of 6-, N-two (2-naphthyl) amido] fluorenes or 1, two [N-(1-the naphthyl)-N-phenyl amido] naphthalenes of 5-.
Another kind of useful electric hole transport material is EP 1,009,041 described polycyclic aromatics, in addition, polymer electricity hole transport material also can be used, as poly-(N-vinylcarbazole) (PVK), Polythiophene, polypyrrole, polyaniline and copolymerized macromolecule, as poly-(3,4-stretches the ethyl dioxy thiophene)/poly-(4-vinylbenzene-sulfonate), be also referred to as PEDOT/PSS.
Luminescent layer (Light-emitting layer, LEL)
Describe as No. the 4th, 769,292, the U.S. and the 5th, 935, No. 721 patent cases, the luminescent layer of organic electroluminescent element is made of a luminous or epipolic material, and this zone also be electronics-electric hole to again in conjunction with and the place that produces electroluminescence; Luminescent layer can be made up of single-material, but usually all is to comprise a main light emission material and an objective luminescent material or any photochromic hotchpotch that can be luminous; Main light emission material in luminescent layer can be an electron transport material (as described below), or an electric hole transport material (as mentioned above), or other materials-electric hole bonded combination of materials again of maybe can powering; Hotchpotch normally is selected from the dyestuff of high fluorescence efficiency, but phosphorescent compound also is spendable as WO 98/55561, WO 00/18851, WO 00/57676 and WO 00/70655 described transition metal complex; The weight percent that hotchpotch is doped in the main light emission material is generally 0.01% to 10%.
One important key is arranged when selecting a dyestuff for hotchpotch, be exactly to compare energy gap current potential (bandgappotential), and the energy gap current potential is the highest molecule orbital (highest occupied molecularorbital) and the minimum difference of not filling up molecule orbital (lowest unoccupied molecular orbital) of filling up of a part, if the efficient energy of wanting to reach from the main light emission material to hotchpotch shifts, then the energy gap of hotchpotch must be less than the energy gap of main light emission material.
Known and host emitter and luminescent material that be used are exposed in the U.S. the 4th, 768, No. 292, the 5th, 141, No. 671, the 5th, 150, No. 006, the 5th, 151, No. 629, the 5th, 405, No. 709, the 5th, 484, No. 922, the 5th, 593, No. 788, the 5th, 645, No. 948, the 5th, 683, No. 823, the 5th, 755, No. 999, the 5th, 928, No. 802, the 5th, 935, No. 720, the 5th, 935, No. 721 and the 6th, 020, No. 078 patent case, but be not limited to above patent.
The metal complex that is constituted with oxine and like derivatives (molecular formula A) is a kind of of useful host emitter compound, particularly is fit to the electroluminescence of emission wavelength greater than 500nm, as green, yellow, tangerine and ruddiness.
9, the derivative (molecular formula B) of 10-two-(2-naphthyl) anthracene particularly is applicable to the electroluminescence of emission wavelength greater than 400nm for constituting host emitter a kind of of usefulness, for example, and blue, green, yellow, tangerine, ruddiness.
Illustration comprises 9,10-two-(2-naphthyl) anthracene and 2-the 3rd-butyl-9,10-two-(2-naphthyl) anthracene; The anthracene derivant that other can be used as the luminescent layer host emitter comprises 9, two [4-(2, the 2-diphenylacetylene) phenyl] anthracene derivant and EP 681, the 019 described phenylanthracene derivatives of 10-.
Being described in diphenylethyllene in the 5th, 121, No. 029 patent case of the U.S., to stretch aryl derivatives also be the effective host emitter that is used for luminescent layer.
The fluorescence hotchpotch that is fit to comprises derived from fusing ring, heterocycle and other compounds for example anthracene, four benzene (tetracene), dibenzopyrans, perylene (perylene), rubrene (rubrene), tonka bean camphor (coumarin), rhodamine (rodamine), quinacridone (quinacridone), thiapyran (thiopyran), polymethine (polymethine), pyrilium, thiapyrilium and carbostyryl compound.Following illustration comprises some available hotchpotchs, but is not limited only to this:
Wherein R can be hydrogen, the tertiary butyl or
N=1 or 2 wherein, R
1, R
2, R
3, R
4Be selected from replace or the phenyl of non-replacement, 1-naphthyl, 2-naphthyl, 9-anthryl or
R
9, R
10, R
11, R
12Be selected from replace or the phenyl of non-replacement, 1-naphthyl, 2-naphthyl, 9-anthryl or
R wherein
13, R
14, X be selected from replace or the phenyl of non-replacement, 1-naphthyl, 2-naphthyl, 9-anthryl or
Wherein R can be hydrogen or the tertiary butyl or
Wherein R can be hydrogen, the tertiary butyl or
Wherein R can be hydrogen, phenyl, methyl or
Wherein, formula eight is 5,6,11,12-tetraphenyl tetracene (rubrene) [5,6,11,12-tetraphenylnaphthacene (rubrene)], be a gold-tinted hotchpotch that is widely studied and uses, according to some research reported in literature (Y.Sato et al, Syn.Met., 1997,91,103), this compound has following advantage as can be known: the quantum yield near 100%, anti-concentration quenching can reach 7%, tool bipolarity or the like, and can increase element stability and life-span.And available general host emitter or electric hole transport material are announced I242595 patent case as its host emitter as Taiwan.
Electron transfer layer (Elctron-transporting layer, ETL)
In this invention, the thin-film material of the electron transfer layer of more suitable organic electroluminescent element is metal-chelating oxine class (oxinoid) compound, comprise oxine (oxine) chelate group, this type of compound can help the injection and the transmission of electronics and produce high-level efficiency and the film shape that is easy to make; Other can be used as electron transport material and comprise the U.S. the 4th, 356, No. 429 disclosed various butadiene derivatives of patent case and the U.S. the 4th, 539, No. 507 described various heterocycle optics brighteners of patent case (heterocyclic opticalbrighteners), and the luxuriant class of benzo-aza also can be used as the available electron transport material.
In some example, luminescent layer and electron transfer layer optionally are merged into simple layer, also can take into account luminous simultaneously and electric transmission.
Negative electrode (Cathode)
If being designed to electroluminescence is appeared by anode, then almost any in this invention conductive material all can be formed negative electrode, wherein comparatively the material behavior of demand is that film-forming properties is good, this can guarantee that negative electrode and beneath organic layer have excellent contact, and then promote the injection of electronics when low voltage, and good stability to be arranged; Useful cathode material be generally low work function metal (＜4.0eV) or metal alloy; The U.S. the 4th, 885, the magnesium silver alloys (Mg:Ag) described in No. 221 patent cases is one of suitable cathode material, wherein Yin ratio is 1% to 20%; Another kind of suitable cathode material is to comprise the two-layer stratigraphic structure that a thick conductive metal layer covers a low workfunction metal thin layer or metal-salt, the U.S. the 5th, 677, and this kind negative electrode described in No. 572 patent cases is made up of a LiF thin layer and an Al thick-layer; Other useful cathode materials including but not limited in U.S. the 5th, 059, No. 861, the 5th, 059, No. 862 and the 6th, 140, No. 763 patent cases the material that disclosed.
And when element design is that electroluminescence is to see through negative electrode to send, then negative electrode is necessary for transparent or approaches transparently, in this case, metal must very thinly maybe must use the transparent conductive oxide or the combination of these materials; The U.S. the 5th, 776, in No. 623 patent cases relevant for the detailed description of optical clear negative electrode; The method of deposition cathode material can be evaporation (evaporation), sputter (sputtering) or chemical vapour deposition (chemical vapor deposition), and in case of necessity, negative electrode can be patterned (patterning), via many modes of knowing, comprise, but be not restricted to: via shade deposition (through-mask deposition), as the U.S. the 5th, 276, No. 380 patent cases and EP 0732868 described whole shadow mask techniques (integral shadowmasking), laser ablation (laser ablation) and selective chemical vapour deposition.
In addition, in order to improve the glow color of OLED, luminous efficiency, stability of photoluminescence, component life and element production method etc. can be consulted U.S. of having given the 4th, 356, No. 429, the 4th, 539, No. 507, the 4th, 720, No. 432, the 4th, 885, No. 211, the 5th, 151, No. 629, the 5th, 150, No. 006, the 5th, 141, No. 671, the 5th, 073, No. 446, the 5th, 061, No. 569, the 5th, 059, No. 862, the 5th, 059, No. 861, the 5th, 047, No. 687, the 4th, 950, No. 950, the 4th, 769, No. 292, the 5th, 104, No. 740, the 5th, 227, No. 252, the 5th, 256, No. 945, the 5th, 069, No. 975, the 5th, 122, No. 711, the 5th, 366, No. 811, the 5th, 126, No. 214, the 5th, 142, No. 343, the 5th, 389, No. 444, patent cases such as the 5th, 458, No. 977.
In another preferred embodiment of the present invention, this OLED is an indicating meter.Generally speaking, this indicating meter can be used for TV, mobil phone, computer monitor, watch-dog, various individual, family, office and/or the employed device of the vehicles and/or electrical appliance or other and can use the device and/or the electrical appliance of indicating meter.
Embodiment
In order to further specify method of the present invention and advantage, below especially exemplified by several synthesis examples and embodiment, but spirit of the present invention and particular content be not as limit.
The introduction of the instrument that this case embodiment can use below is provided:
1. nuclear magnetic resonance spectrometer:, and be the measurement standard compound with CDCl3 for VARIAN Unity 300MHz measures obtaining nucleus magnetic resonance (NMR) spectrum.
2. mass spectrograph: be with MICROMASS TRIO-2000GC/MS and use the free method of quick atomic collision (FAB) to measure.
3. film under vacuum evaporator (coater): be 18 o'clock rotary evaporators with TRC, it can place 6 substrates, 2 motor-driven baffle plates, 8 electric crucibles, 5 concussion inductor blocks, IC-5 film-thickness monitoring and diffusion types group Pus.
4. spectrophotometer (colorimeter): be to use PhotoResearch PR-650 instrument to measure.
5. power supply unit (programmable power supply): be to use KEITHLEY 2400 instruments to supply with electric current.
I. compound is synthetic
Synthetic comparative example one:
Method is with synthesis example one, and wherein 2-methylanthracene makes 2-ethylanthracene into, gets 9-bromo-2-ethylanthracene (yellow powder 4g, productive rate 57.8%, HPLC＞96%).
Synthetic comparative example two:
Method is with synthesis example one, and wherein 2-methylanthracene makes 2-t-butylanthracene into, gets 9-bromo-2-t-butylanthracene (yellow powder 2.5g, productive rate 37.5%, HPLC＞96%).
We find the bromination of 2-methyl anthracene, and productive rate is high especially, but can further obtain the OLED material of high purity and mass production.
Synthesis example one:
Get the 500ml three-necked bottle, add methylene dichloride (30ml), (5g, 25mmole), (28mmole), normal temperature stirs down for N-Bromosuccinimide, 4.8g to add NBS again to add 2-methylanthrancene.Detect whether to react with HPLC and finish, after reacting completely, pour in the water and separate out.Filter the back with the small amount of methanol flushing, get 9-bromo-2-methylanthrancene (deep yellow powder 3g, productive rate 70%, HPLC＞96%).
1H?NMR(CDCl
3，300MHz，δ)：8.53(d，1H)；8.27(s，1H)；8.21(s，1H)；7.87(d，1H)；7.75(d，1H)；7.58(t，1H)；7.45(t，1H)；7.24(d，1H)；2.60(s，3H)。
Synthesis example two to four can cooperate referring to following chemical equation:
Synthesis example two:
Get the 500ml three-necked bottle, add methylene dichloride (30ml), (5g, 25mmole), (28mmole), normal temperature stirs down for N-Bromosuccinimide, 4.8g to add NBS again to add 2-methylanthracene.Detect whether to react with TLC and finish, after reacting completely, pour in the water and separate out.Filter the back with the small amount of methanol flushing, get intermediate A 1 (deep yellow powder 3g, HPLC＞96%).
1H?NMR(CDCl
3，300MHz，δ)：8.53(d，1H)；8.27(s，1H)；8.21(s，1H)；7.87(d，1H)；7.75(d，1H)；7.58(t，1H)；7.45(t，1H)；7.24(d，1H)；2.60(s，3H)。
Synthesis example three:
Get the 500ml three-necked bottle, add Toluene (100ml)/Ethanol (20ml)/D.I.water (35ml), (20g, 0.074mol), (14g 0.081mol), then adds K to add 1-Naphthaleneboronic acid again to add intermediate A 1
2CO
3(20.6g, 0.143mo1) after, add Pd (pph at once
3)
4(0.3% * 0.074mo1).Whether be heated to 100～105 ℃, refluxing to detect to react in back 2 hours finishes.After reaction is finished, pour in the water back into the toluene extraction, the extraction back dewaters with sodium sulfate.Filter, behind the concentrating under reduced pressure, get intermediate A 2 (the dense thick liquid 20g of tawny, productive rate 84%, HPLC＞95%).
1H?NMR(CDCl
3，300MHz，δ)：8.52(s，1H)；8.02-7.96(m，4H)；7.85-7.81(m，1H)；7.69-7.63(dd，1H)；7.51-6.79(m，8H)；2.27(s，3H)。
Synthesis example four:
Get the 500ml three-necked bottle, add methylene dichloride (40m1)/Acetic acid (150m1), (20g 0.063mol), carries out ice bath then to add intermediate A 2.After waiting to reduce to 0～5 ℃, (11.2g 0.07mol) slowly splashes in the three-necked bottle, goes after dripping off again and removes ice bath with Br2 with the 50ml filling tube.After reacting completely, pour in the water, pour in the reactant with Na2SO3 (aq) 20wt% again, no longer change, stir after 30 minutes until aqueous solution color.Filter.Get intermediate A 3 (yellow-green colour powder 22g, productive rate 88%, HPLC＞95%).
1H?NMR(CDCl
3，300MHz，δ)：8.61(d，1H0；8.53(d，1H)；8.06(d，1H)；8.01(d，1H)，7.71-7.30(m，7H)；7.22-7.02(m，3H)；2.33(s，3H)。
Synthesis example five:
Method with synthesis example three use intermediate A 1 (16g, 0.06mol) (11.2g 0.066mol) carries out the Suzuki coupled reaction with 2-Naphthaleneboronic acid, can get intermediate A 4, output 20g (the dense thick liquid of tawny, productive rate 84%, HPLC＞95%).
1H?NMR(CDCl
3，300MHz，δ)：8.54(s，1H)；8.10-8.06(m，3H)；8.01(d，1H)；7.97(s，1H)；7.96-7.94(m，1H)；7.96-7.94(m，1H)；7.77(d，1H)；7.67-7.62(m，3H)；2.44(s，3H)。
Synthesis example six:
Method is used intermediate A 4 with synthesis example four, and (20g 0.06mol) can get intermediate A 5, output 20g (yellow-green colour powder, productive rate 84%, HPLC＞95%).
1H?NMR(CDCl
3，300MHz，δ)：8.59(d，1H)；8.52(d，1H)；7.96(d，1H)；7.94(d，1H)；7.87(d，1H)；7.86(s，1H)；7.61-7.48(m，5H)；7.47(d，1H)；7.42(s，1H)；7.30(dt，1H)；2.36(s，3H)。
Synthesis example seven:
Method with synthesis example three use intermediate A 1 (10g, 0.037mol) (10g 0.041mol) carries out the Suzuki coupled reaction with 4-(2-Naphthalene) bezeneboronic acid, can get intermediate A 6, output 12g (pale yellow powder, productive rate 84%, HPLC＞95%).
1H?NMR(CDCl
3，300MHz，δ)：δ：8.49(s，1H)；8.26(s，1H)；8.06(d，1H)；8.01-7.93(m，7H)；7.77(d，1H)；7.59-7.53(m，5H)；7.47(dt，1H)；7.38(dd，1H)；7.37(d，1H)；2.57(s，3H)。
Synthesis example eight:
Method is used intermediate A 6 with synthesis example four, and (9.2g 0.023mol) can get intermediate A 7, output 10g (yellow-green colour powder, productive rate 84%, HPLC＞95%).
1H?NMR(CDCl
3，300MHz，δ)：8.61(d，1H)；8.54(d，1H)；8.02-7.90(m，7H)；7.72(d，1H)；7.59-7.50(m，5H)；7.44(d，1H)；7.38(dt，1H)；2.46(s，3H)。
Synthesis example nine: B601 preparation
Get the 500ml three-necked bottle, toluene (100ml)/ethanol (20ml)/D.I.water (35ml), (7g, 17.6mmol), (5g 20.1mmol), then adds K to add 4-(2-Naphthyl) phenylboronic acid again to add intermediate A 3
2CO
3(5g, 35.7mmol) after, add Pd (pph at once
3)
4(0.3% * 17.6mmol).Whether be heated to backflow (about 100～105 ℃), refluxing to detect to react in back 2 hours finishes.After reaction is finished, pour in the water back into the toluene extraction, the extraction back dewaters with sodium sulfate.Filter, lead to the chromatography tubing string, again behind the concentrating under reduced pressure.Filter, get 7.3g pale yellow powder (productive rate 80%, HPLC＞99%).
1H?NMR(CDCl
3，300MHz，δ)：8.22(s，1H)；8.08-7.83(m，9H)；7.72(dt，1H)，7.58-7.51(m，3H)；7.30-7.19(m，6H)；7.08-7.04(m，2H)；6.79(d，1H)；6.65(s，1H)；2.08(s，3H).T
d(TGA)：421.83℃；Tm(DSC)265.90℃；λ
abs(nm)：358，377，397；λ
em(nm)：425；MF：C
41H
28；m/e(Mass，M
+)：520.67。
Synthesis example ten: B602 preparation
Method is used intermediate A 3 (2g with synthesis example nine, 5.03mmol) use 4-(1-Naphthal) phenylboronic acid (1.4g, 5.6mmol) carry out the Suzuki coupled reaction, can get B602, output 1.1g pale yellow powder (productive rate 42%, HPLC＞95%).
1H?NMR(CDCl
3，300MHz，δ)：8.22-8.20(m，1H)；8.07(d，1H)；8.00(d，1H)；7.98-7.87(m，2H)；7.85(d，1H)；7.82(d，1H)；7.78-7.68(m，4H)；7.68-7.55(m，10H)；7.52-7.51(dt，2H)；7.38(d，1H)；7.37-7.35(dt，1H)；2.30(s，3H)。T
d(TGA)：407.18℃；Tm(DSC)221.37℃；λ
abs(nm)：358，377，398；λ
em(nm)：423；MF：C
41H
28；m/e(Mass，M
+)：520.67。
Synthesis example 11: B603 preparation
Method is used intermediate A 3 with synthesis example nine, and (2g, (1.1g 5.5mmol) carries out the Suzuki coupled reaction, can get B603, the faint yellow last powder of output 1.4g (productive rate 58%, HPLC＞95%) 5.03mmol) to use 4-Biphenylboronic acid.
1H?NMR(CDCl
3，300MHz，δ)：8.13(d，1H)；8.11(d，1H)；7.93(t，2H)；7.88-7.82(m，3H)；7.81-7.76(m，3H)；7.70(m，1H)；7.67-7.42(m，8H)；7.38(dt，1H)；7.28-7.23(m，3H)；2.35(s，3H)。T
d(TGA)：391.70℃；Tm(DSC)239.31℃；λ
abs(nm)：358，377，398；λ
em(nm)：424；MF：C
37H
26；m/e(Mass，M
+)：470.61。
Synthesis example 12: B604 preparation
Method is used intermediate A 3 with synthesis example nine, and (2g, (1.2g 7.0mmol) carries out the Suzuki coupled reaction, can get B604, output 1.3g pale yellow powder (productive rate 58%, HPLC＞95%) 5.03mmol) to use 2-Naphthaleneboronicacid.
1H?NMR(CDCl
3，300MHz，δ)：8.20-8.09(m，6H)；8.02(t，1H)；7.85-7.63(m，7H)；7.57(t，1H)；7.46(d，1H)；7.37-7.22(m，4H)；2.36(s，3H)。T
d(TGA)：373.70℃；λ
abs(nm)：358，377，397；λ
em(nm)：423；MF：C
35H
24；m/e(Mass，M
+)：444.58。
Synthesis example 13: B605 preparation
Get the 500ml three-necked bottle, add toluene (40ml)/ethanol (8ml)/D.I.water (15ml), (4g, 10mmole), (2.8g 11mmole), then adds K to add 4-(2-Naphthal) phenylboronic acid again to add intermediate A 5
2CO
3(2.8g, 20mmol) after, add Pd (pph at once
3)
4(0.3% * 10mmole).Whether be heated to about 100～105 ℃ of reflux temperature, refluxing to detect to react in back 2 hours finishes.After reaction is finished, pour in the water back into Toluene 100～150ml extraction, the extraction back is with Na
2SO
4Dewater.Filter, lead to the chromatography tubing string, behind the concentrating under reduced pressure, separate out again.Filter, get B605, output 3.9g pale yellow powder (tight rate 74%, HPLC＞95%).
1H?NMR(CDCl
3，300MHz，δ)：8.25(s，1H)；8.10(d，1H)；8.06-7.92(m，9H)；7.83(d，1H)；7.76(d，1H)；7.70(d，1H)；7.63-7.58(m，5H)；7.56-7.52(m，2H)；7.48(s，1H)；7.36-7.29(m，2H)；7.24-7.22(dd，1H)；2.37(s，3H)。T
d(TGA)：460.14℃；Tm(DSC)248.13℃；λ
abs(nm)：358，378，398；λ
em(nm)：431；MF：C
41H
28；m/e(Mass，M
+)：520.67。
Synthesis example 14: B606 preparation
Method is used intermediate A 5 with synthesis example 13, and (4g, 10mmol) (2.2g 11mmol) carries out the Suzuki coupled reaction, can get B606, output 3.6g pale yellow powder (productive rate 76%, HPLC＞95%) with 4-Biphenylboronic acid.
1H?NMR(CDCl
3，300MHz，δ)：8.10-7.89(m，4H)；7.86(d，2H)；7.76(d，2H)；7.71-7.59(m，10H)；7.53(s，1H)；7.50(t，1H)；7.41-7.30(m，2H)；7.24(dd，1H)；2.36(s，3H)。T
d(TGA)：434.51℃；Tm(DSC)248.13℃；λ
abs(nm)：359，378，398；λ
em(nm)：429；MF：C
37H
26；m/e(Mass，M
+)：470.61。
Synthesis example 15: B607 preparation
Method is used intermediate A 5 with synthesis example 13, and (4g, 10mmol) (2.8g 11mmol) carries out the Suzuki coupled reaction, can get B607, output 3.4g pale yellow powder (productive rate 65%, HPLC＞90%) with 4-(1-Naphthal) phenylboronic acid.
1H?NMR(CDCl
3，300MHz，δ)：8.19(dd，1H)；8.09(d，2H)；8.06-8.03(m，2H)；8.01(s，1H)；7.99-7.97(dd，2H)；7.96-7.93(m，3H)；7.88-7.86(m，2H)；7.84(s，1H)；7.83-7.79(m，2H)；7.77-7.75(m，3H)；7.40-7.37(dt，3H)；7.34-7.31(m，2H)；7.28(dd，1H)；7.23-7.21(m，1H)；2.39(s，3H)。T
d(TGA)：433.41℃；Tm(DSC)385.87℃；λ
abs(nm)：360，378，398；λ
em(nm)：429；MF：C
41H
28；m/e(Mass，M
+)：520.67。
Synthesis example 16: B608 preparation
Get the 500ml three-necked bottle, add toluene (40ml)/ethanol (8ml)/D.I.water (15ml), (4.7g, 10mmole), (2.1g 11mmol), then adds K to add 1-Naphthaleneboronic acid again to add intermediate A 7
2CO
3(2.8g, 20mmol) after, add Pd (pph at once
3)
4(0.3% * 10mmole).Whether be heated to about 100～105 ℃ of reflux temperature, refluxing to detect to react in back 2 hours finishes.After reaction is finished, pour in the water back into Toluene 100～150ml extraction, the extraction back is with Na
2SO
4Dewater.Filter, lead to the chromatography tubing string, behind the concentrating under reduced pressure, separate out again.Filter, get B608, output 5.02g pale yellow powder (productive rate 80%, HPLC＞95%).
1H?NMR(CDCl
3，300MHz，δ)：8.29(s，1H)；8.04(d，1H)；8.01-7.97(m，6H)；7.93(d，1H)；7.83(d，1H)；7.72-7.69(m，2H)；7.64(d，1H)；7.61-7.47(m，5H)；7.45(d，1H)；7.39(s，1H)；7.33(dt，1H)；7.25-2.22(m，3H)；7.09(dd，1H)；2.42(s，3H)。T
d(TGA)：442.19℃；Tm(DSC)203.83℃；λ
abs(nm)：359，377，397；λ
em(nm)：426；MF：C
41H
28；m/e(Mass，M
+)：520.67。
II. the color and the brightness measuring of The compounds of this invention institute composed component
A specific embodiment of OLED of the present invention (OLED, 10) is that simplification sectional view with Fig. 1 is for illustrating.OLED 10 comprises a slice transparent glass or plastic rubber substrate 11, and a transparent conductive anode layer 12 is deposited on the plane of base material 11, will be by there being dynamo-electric hole injecting material to be deposited on the surface of anode layer 12, to form electric hole input horizon 13.To have dynamo-electric hole transport layer material to be deposited on electric hole input horizon 13 surfaces again goes up to be formed with dynamo-electric hole transport layer 14.To be caused an organic luminous layer 15 to be deposited on the surface of dynamo-electric hole transport layer 14 by the main light emission material that contains the fluorescence hotchpotch.The electron transfer layer 16 that electron transport material caused is deposited on the surface of organic luminous layer 15.Then the electron injecting layer 17 that the electronics injecting material caused is deposited on the surface of electron transfer layer 16 and metal conducting layer 18 is deposited on the surface of electron injecting layer 17 and forms cathode layer 18.
In this specific embodiment, conductive anode layer 12 is p type point of contact, and conductive cathode layer 18 is n type point of contact.The negative terminal of power supply 19 is connected to conductive layer 18 and positive terminal is connected to conductive layer 12.When current potential mat power supply 19 is applied between conductive anode layer 12 and the conductive cathode layer 18, then will will enter in the organic luminous layer 15 and will be by electron injecting layer 17 and organic electron transport layer 16 from n type point of contact [conductive cathode layer 18] institute injected electrons from electric hole that p type point of contact [conductive anode layer 12] injected by dynamo-electric hole input horizon 13 being arranged and having dynamo-electric hole transport layer 14 to enter organic luminous layer 15.At organic luminous layer 15, when electronics combines with electric hole again, ballistic phonon then.
Its production process is as follows:
One, the cleaning of substrate: prepare the good ito substrate of etching (this ito substrate is of a size of the 40x40mm size), this ito substrate is inserted in the baking oven after with acetone, methyl alcohol and washed with de-ionized water, with 130 ℃ temperature bakings 1 hour;
Two, the pre-treatment of substrate: insert after ito substrate taken out in baking oven in the electricity slurry treater, activate according to existing activation step;
Three, evaporation: the ito substrate that pre-process is finished is positioned on the rotation carrier in the TRC evaporation board, when the vacuum tightness of evaporator cavity reaches 10
-6During Torr, begin to heat deposition material, the evaporation speed of this moment then is to be monitored by quartzy sensor.The contriver with
Speed evaporation electricity hole input horizon, with
Speed evaporation NPB, with
Speed evaporating Al q
3, again with
Speed evaporation LiF, and with
The speed evaporating Al.
Four, component package: cap is the glass material.After glass cover coated UV glue, the element of just having made is put into nitrogen glove box with cap, with weight ito substrate and cap driving fit are got up again, and carry out the polyreaction of glue with UV light.
Five, the measurement of element color and brightness: with packaged element, under the control of LabVIEW formula, supply with electric current with power supply unit, and with spectrophotometer measuring element spectrum, brightness and luminescent chromaticity (CIE
X, y) etc. character.
According to the measuring method of aforementioned color and brightness, the contriver measures color and the brightness of compound as organic luminous layer institute composed component respectively, and its result is as follows:
Embodiment 1 (Comparative Example)
ITO (indium tin oxide) glass substrate is the thick 0.7mm of the wide 40mmx of long 40mmx, in methyl alcohol, cleaned 12 minutes via ultrasound, and then through ultraviolet ray (generation ozone) irradiation 10 minutes.With the glass substrate shift-in vacuum vapor deposition equipment after being cleaned.Having on the surface of transparency electrode, it is 180nm that formation thin film S707 (please referring to following structural formula) has thickness, makes the film cover transparency electrode of formation.The formed film of S707 is as the first electric hole input horizon (electric hole transport layer).On S707, form the NPB (please referring to following structural formula) of 7nm then.Formed film is the second electric hole input horizon (an electric hole transport layer).With the compound of 2% formula 17 and the compound vacuum vapor deposition of ADN, form thickness 30nm as luminescent layer.Forming a thickness with Alq (please referring to following structural formula) again is that the 10nm film is as electron injecting layer.After, 0.1nm is deposited on the Alq with lithium fluoride (LiF), as electron injecting layer (negative electrode).At last aluminium is formed negative electrode, the deposition of above-mentioned sequence finishing device with vapour deposition 150nm.Then, with this device enclosed package in a dry glove box to protect.
With current density 20mA/cm
2When driving electromechanical excitation light dipolar body, driving voltage is 6.69V, and sending blue light, CIE (0.159,0.251), brightness is 2237cd/m
2, luminous efficiency is 11.18cd/A.Under room temperature with 20mA/cm
2The element of running made is to be used to operate stability test.Running 300 brightness as a child descend 25%.
Embodiment 2 (Comparative Example)
Electromechanical excitation light dipolar body is made, and according to the program of embodiment one, replaces the ADN compound with compound MADN.
With current density 20mA/cm
2When driving electromechanical excitation light dipolar body, driving voltage is 6.45V, and sending blue light, CIE (0.154,0.228), brightness is 1937cd/m
2, luminous efficiency is 9.68cd/A.Running 300 brightness as a child descend 20%.
Embodiment 3 (invention example)
Electromechanical excitation light dipolar body is made, and according to the program of embodiment one, replaces the ADN compound with compound B-26 01.
With current density 20mA/cm
2When driving electromechanical excitation light dipolar body, driving voltage is 6.46V, and sending blue light, CIE (0.157,0.242), brightness is 2146cd/m
2, luminous efficiency is 10.73cd/A.Running 300 brightness as a child descend 18%.
Embodiment 4 (invention example)
Electromechanical excitation light dipolar body is made, and according to the program of embodiment one, replaces the ADN compound with the compound with formula B603.
With current density 20mA/cm
2When driving electromechanical excitation light dipolar body, driving voltage is 6.78V, and sending blue light, CIE (0.163,0.234), brightness is 1890cd/m
2, luminous efficiency is 9.45cd/A.Running 300 brightness as a child descend 16%.
Embodiment 5 (invention example)
Electromechanical excitation light dipolar body is made, and according to the program of embodiment one, replaces the ADN compound with the compound with formula B605.
With current density 20mA/cm
2When driving electromechanical excitation light dipolar body, driving voltage is 6.60V, and sending blue light, CIE (0.155,0.238), brightness is 2043cd/m
2, luminous efficiency is 10.22cd/A.Running 300 brightness as a child descend 16%.
Embodiment 6 (invention example)
Electromechanical excitation light dipolar body is made, and according to the program of embodiment one, replaces the AND compound with the compound with formula B606.
With current density 20mA/cm
2When driving electromechanical excitation light dipolar body, driving voltage is 6.44V, and sending blue light, CIE (0.158,0.234), brightness is 2028cd/m
2, luminous efficiency is 10.14cd/A.Running 300 brightness as a child descend 14%.
Embodiment 7 (invention example)
With the pre-treatment of embodiment one same way as, it is 90nm that formation thin film S707 has thickness, makes the film cover transparency electrode of formation.The formed film of S707 is as the first electric hole input horizon (electric hole transport layer).On S707, form the NPB of 7nm then.Formed film is the second electric hole input horizon (an electric hole transport layer).With the compound of 0.5%RD5,60% rubrene (rubrene) and 40% B601 compound vacuum vapor deposition, form thickness 50nm as luminescent layer.Forming a thickness with Alq again is that the 45nm film is as electron injecting layer.After, 0.1nm is deposited on the Alq with lithium fluoride (LiF), as electron injecting layer (negative electrode).At last aluminium is formed negative electrode, the deposition of above-mentioned sequence finishing device with vapour deposition 150nm; Then, with this device enclosed package in a dry glove box to protect.
With current density 20mA/cm
2When driving electromechanical excitation light dipolar body, driving voltage is 7.56V, and sending red light, CIE (0.642,0.349), brightness is 1257cd/m
2, luminous efficiency is 6.28cd/A.Running 300 brightness as a child descend 6%.
Embodiment 8 (invention example)
With the pre-treatment of embodiment one same way as, it is 75nm that formation thin film S707 has thickness, makes the film cover transparency electrode of formation.The formed film of S707 is as the first electric hole input horizon (electric hole transport layer).On S707, form the NPB of 7nm then.Formed film is the second electric hole input horizon (an electric hole transport layer).Compound and the compound vacuum vapor deposition with formula B601 with 5%GD54 form thickness 30nm as luminescent layer.Forming a thickness with Alq again is that the 25nm film is as electron injecting layer.After, 0.1nm is deposited on the Alq with lithium fluoride (LiF), as electron injecting layer (negative electrode).At last aluminium is formed negative electrode, the deposition of above-mentioned sequence finishing device with vapour deposition 150nm.Then, with this device enclosed package in a dry glove box to protect.
With current density 20mA/cm
2When driving electromechanical excitation light dipolar body, driving voltage is 5.78V, and sending green light, CIE (0.329,0.627), brightness is 4445cd/m
2, luminous efficiency is 22.23cd/A.Running 300 brightness as a child descend 8%.
Embodiment 9 (invention example)
With the pre-treatment of embodiment one same way as, it is 180nm that formation thin film S707 has thickness, makes the film cover transparency electrode of formation.The formed film of S707 is as the first electric hole input horizon (electric hole transport layer).On S707, form the NPB of 7nm then.Formed film is the second electric hole input horizon (an electric hole transport layer).Compound and the compound vacuum vapor deposition with formula B601 with 3%BD5 form thickness 30nm as luminescent layer.Forming a thickness with Alq again is that the 10nm film is as electron injecting layer.After, 0.1nm is deposited on the Alq with lithium fluoride (LiF), as electron injecting layer (negative electrode).At last aluminium is formed negative electrode, the deposition of above-mentioned sequence finishing device with vapour deposition 150nm.Then, with this device enclosed package in a dry glove box to protect.
With current density 20mA/cm
2When driving electromechanical excitation light dipolar body, driving voltage is 6.34V, and sending dark blue coloured light, CIE (0.142,0.141), brightness is 1131cd/m
2, luminous efficiency is 5.65cd/A.Running 300 brightness as a child descend 15%.
Embodiment 10 (invention example)
With the pre-treatment of embodiment one same way as, it is 75nm that formation thin film S707 has thickness, makes the film cover transparency electrode of formation.The formed film of S707 is as the first electric hole input horizon (electric hole transport layer).On S707, form the NPB of 7nm then.Formed film is the second electric hole input horizon (an electric hole transport layer).Compound and the compound vacuum vapor deposition with formula B601 with 3%TBRb form thickness 30nm as luminescent layer.Forming a thickness with Alq again is that the 25nm film is as electron injecting layer.After, 0.1nm is deposited on the Alq with lithium fluoride (LiF), as electron injecting layer (negative electrode).At last aluminium is formed negative electrode, the deposition of above-mentioned sequence finishing device with vapour deposition 150nm.Then, with this device enclosed package in a dry glove box to protect.
With current density 20mA/cm
2When driving electromechanical excitation light dipolar body, driving voltage is 6.56V, and sending sodium yellow, CIE (0.477,0.496), brightness is 2480cd/m
2, luminous efficiency is 12.40cd/A.Running 300 brightness as a child descend 11%.
Embodiment 11 (invention example)
With the pre-treatment of embodiment one same way as, it is 75nm that formation thin film S707 has thickness, makes the film cover transparency electrode of formation.The formed film of S707 is as the first electric hole input horizon (electric hole transport layer).The film that the compound of 2%TBRb and NPB is formed thickness 20nm then on S707 is the second electric hole input horizon (an electric hole transport layer).Compound and the compound vacuum vapor deposition with formula B601 with 2% formula 17 form thickness 40nm as luminescent layer.Forming a thickness with Alq again is that the 10nm film is as electron injecting layer.After, 0.1nm is deposited on the Alq with lithium fluoride (LiF), as electron injecting layer (negative electrode).At last aluminium is formed negative electrode, the deposition of above-mentioned sequence finishing device with vapour deposition 150nm.Then, with this device enclosed package in a dry glove box to protect.
With current density 20mA/cm
2When driving electromechanical excitation light dipolar body, driving voltage is 7.35V, and sending white light, CIE (0.318,0.317), brightness is 2710cd/m
2, luminous efficiency is 13.55cd/A.Running 300 brightness as a child descend 14%.
And, make a comparison sheet with regard to driving voltage, brightness, current efficiency, colourimetric number (CIE) with regard to the various embodiments described above and the formed electromechanical excitation light dipolar body of comparative example, please referring to shown in the following table one:
Table one
Confirm from above-mentioned table one embodiment: when the main body of luminescent layer through selecting when comprising the asymmetric three 2-methyl anthracene compounds that replace anthracenes and be the luminescent layer main body the very big improvement that can reach voltage, efficient and stability.In addition, as can obviously finding out, but comprise the colour purity of asymmetric three holding elements when replacing the 2-methyl anthracene compound of anthracenes when the main body of luminescent layer from the CIE coordinate.Fig. 2 A, Fig. 2 B, Fig. 2 C and Fig. 2 D, after this series compound was made into element, embodiment one compares with comparative example one can reduce driving voltage 0.23V.Embodiment one compares with comparative example two can increase by about 10% luminous efficiency.Electromechanical excitation light dipolar body utilizes compound formula B601 of the present invention～formula B607, and the present invention has high efficiency luminous, and sends blue light (as Fig. 2 C).And can be used as luminous main body (as Fig. 2 D) red, blue, green, gold-tinted.
With the organic molecule is the electromechanical excitation light dipolar body of material made, and material itself (existing in the uniform thin film mode) is wanted and can be avoided crystallization in element operation (current flowing) process.The crystallization meeting causes molecule to stack, and is that the electroluminescence (electroluminescence) of fluorescence or phosphorescence essence all can decline to a great extent element brightness by quenching (quenching), eventually to not working fully.So make electromechanical excitation light dipolar body, its composition material is on molecular designing, make every effort to the vitreous state of amorphism (amorphous), be respectively ADN without anneal shown in Fig. 3 A, Fig. 3 B, Fig. 3 C, by scan-type microscope measured 5,000 times, 50,000 times, 100,000 times film surface form.And be respectively ADN shown in Fig. 4 A, Fig. 4 B, Fig. 4 C, under atmosphere, 90 ℃, hold temperature after 1 hour, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope.Be respectively MADN shown in Fig. 5 A, Fig. 5 B, Fig. 5 C, without anneal, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope.And be respectively MADN shown in Fig. 6 A, Fig. 6 B, Fig. 6 C, under atmosphere, 90 ℃, hold temperature after 1 hour, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope.Be respectively formula B601 compound shown in Fig. 7 A, Fig. 7 B, Fig. 7 C, without anneal, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope.And be respectively formula B601 compound shown in Fig. 8 A, Fig. 8 B, Fig. 8 C, under atmosphere, 90 ℃, hold temperature after 1 hour, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope.Be respectively formula B603 compound shown in Fig. 9 A, Fig. 9 B, Fig. 9 C, without anneal, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope.And be respectively formula B603 compound shown in Figure 10 A, Figure 10 B, Figure 10 C, under atmosphere, 90 ℃, hold temperature after 1 hour, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope.Be respectively formula B605 compound shown in Figure 11 A, Figure 11 B, Figure 11 C, without anneal, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope.And be respectively formula B605 compound shown in Figure 12 A, Figure 12 B, Figure 12 C, under atmosphere, 90 ℃, hold temperature after 1 hour, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope.Be respectively formula B606 compound shown in Figure 13 A, Figure 13 B, Figure 13 C, without anneal, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope.And be respectively formula B606 compound shown in Figure 14 A, Figure 14 B, Figure 14 C, under atmosphere, 90 ℃, hold temperature after 1 hour, by the film surface form of measured 5,000 times, 50,000 times, 100,000 times in scan-type microscope.
Wherein, shown in Fig. 3 A, Fig. 3 B, Fig. 3 C, during without anneal, this film promptly has crystalline form is obviously arranged; Shown in Fig. 4 A, Fig. 4 B, Fig. 4 C, after anneal, this thin film crystallization form is even more serious; Fig. 5 A, Fig. 5 B, Fig. 5 C and Fig. 6 A, Fig. 6 B, Fig. 6 C compare down demonstration, and film surface is level and smooth during without anneal, but this film has slight crystalline form after anneal, and MADN still has minor defects.But shown in figure A, the B of Fig. 7, Fig. 8, Fig. 9, Figure 10, Figure 11, Figure 12, Figure 13, Figure 14, the C, no matter have or not annealed processing, this film is all level and smooth and the noncrystalline form of tool.Show that the series compound of the structure with formula (I) effectively improves the crystallinity situation of AND, MADN, is good amorphism (amorphous) compound.
Table two
| The film smoothness | Amorphism | |
| AND (comparative) | △ | △ |
| MADN (comparative) | □ | □ |
| B601 (invention) | ○ | ○ |
| B603 (invention) | ○ | ○ |
| B605 (invention) | ○ | ○ |
| B606 (invention) | ○ | ○ |
Zero: very good; : good; △: abominable.
The above only is preferred embodiment of the present invention, only is illustrative for the purpose of the present invention, and nonrestrictive.Those skilled in the art is understood, and can carry out many changes to it in the spirit and scope that claim of the present invention limited, revise, even equivalence, but all will fall within the scope of protection of the present invention.
Claims (21)
1. one kind has the 2-methyl anthracene compound that asymmetric three of novel formula (I) replaces anthracene:
Wherein, X is the aromatic yl group of 6 to 20 replacements that carbon atom is formed of aromatic base carbon number or non-replacement, and Y is the aromatic yl group of 6 to 20 replacements that carbon atom is formed of aromatic base carbon number or non-replacement, and X is not equal to Y.
2. OLED, it comprises:
One substrate;
Two electrodes, wherein an electrode is arranged on this substrate; And
One organic layer, it is arranged between the described electrode, and comprise the have formula 2-methyl anthracene compound of structure of (I), wherein, X is the aromatic yl group of 6 to 20 replacements that carbon atom is formed of aromatic base carbon number or non-replacement, Y is the aromatic yl group of 6 to 20 replacements that carbon atom is formed of aromatic base carbon number or non-replacement, and X is not equal to Y.
3. OLED as claimed in claim 2, wherein this 2-methyl anthracene compound is selected from the group that is made up of following compound:
4. as claim 2 or 3 described OLEDs, wherein this organic layer includes an electric hole input horizon, an electric hole transport layer, an organic luminous layer, an electron transfer layer and an electron injecting layer in regular turn from nearly substrate to the direction away from substrate, and this 2-methyl anthracene compound with structure of formula (I) is contained in the wherein stratiform structure of this electricity hole input horizon, this electricity hole transport layer, this organic luminous layer, this electron transfer layer or this electron injecting layer.
5. OLED as claimed in claim 4, wherein this 2-methyl anthracene compound with structure of formula (I) is contained in this organic luminous layer.
6. as claim 2 or 3 described OLEDs, wherein the thickness of this organic layer is not more than 500nm.
7. OLED as claimed in claim 4, wherein the thickness of this organic layer is not more than 500nm.
8. OLED as claimed in claim 5, wherein the thickness of this organic layer is not more than 500nm.
9. OLED as claimed in claim 6, wherein this OLED is a display equipment.
10. OLED as claimed in claim 6, wherein this OLED is a white light illumination device.
11. OLED as claimed in claim 7, wherein this OLED is a display equipment.
12. OLED as claimed in claim 7, wherein this OLED is a white light illumination device.
13. OLED as claimed in claim 8, wherein this OLED is a display equipment.
14. OLED as claimed in claim 8, wherein this OLED is a white light illumination device.
15. as claim 2 or 3 described OLEDs, wherein this OLED system sends redness, blueness, green, yellow or white light.
16. OLED as claimed in claim 9, wherein this indicating meter sends redness, blueness, green, yellow or white light.
17. OLED as claimed in claim 10, wherein this indicating meter sends redness, blueness, green, yellow or white light.
18. OLED as claimed in claim 11, wherein this indicating meter sends redness, blueness, green, yellow or white light.
19. OLED as claimed in claim 12, wherein this indicating meter sends redness, blueness, green, yellow or white light.
20. OLED as claimed in claim 13, wherein this indicating meter sends redness, blueness, green, yellow or white light.
21. OLED as claimed in claim 14, wherein this indicating meter sends redness, blueness, green, yellow or white light.
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| TW200610801A (en) * | 2004-09-21 | 2006-04-01 | Chin-Hsin Chen | Novel blue organic compound and organic electroluminescent device using the same |
| TW200846442A (en) * | 2007-05-18 | 2008-12-01 | Chin-Hsin Chen | Novel blue organic compound and organic electroluminescent device using the same |
| KR100901887B1 (en) * | 2008-03-14 | 2009-06-09 | (주)그라쎌 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| TW200925138A (en) * | 2007-12-06 | 2009-06-16 | E Ray Optoelectronics Tech Co | Organic electroluminescent devices using anthracene derivative |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200610801A (en) * | 2004-09-21 | 2006-04-01 | Chin-Hsin Chen | Novel blue organic compound and organic electroluminescent device using the same |
| TW200846442A (en) * | 2007-05-18 | 2008-12-01 | Chin-Hsin Chen | Novel blue organic compound and organic electroluminescent device using the same |
| TW200925138A (en) * | 2007-12-06 | 2009-06-16 | E Ray Optoelectronics Tech Co | Organic electroluminescent devices using anthracene derivative |
| KR100901887B1 (en) * | 2008-03-14 | 2009-06-09 | (주)그라쎌 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
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