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WO2011021803A2 - Composé présentant une structure thianthrène, dispositif organique émettant de la lumière et terminal comprenant ledit dispositif - Google Patents

Composé présentant une structure thianthrène, dispositif organique émettant de la lumière et terminal comprenant ledit dispositif Download PDF

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WO2011021803A2
WO2011021803A2 PCT/KR2010/005245 KR2010005245W WO2011021803A2 WO 2011021803 A2 WO2011021803 A2 WO 2011021803A2 KR 2010005245 W KR2010005245 W KR 2010005245W WO 2011021803 A2 WO2011021803 A2 WO 2011021803A2
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WO2011021803A3 (fr
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박정환
김대성
박용욱
김기원
정화순
김원삼
변지훈
최대혁
김동하
홍철광
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Duksan Hi Metal Co Ltd
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    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • Y02E10/00—Energy generation through renewable energy sources
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    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a compound having a thianthrene structure, an organic electric device using the same, and a terminal thereof.
  • organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
  • An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween.
  • the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  • Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their functions.
  • the light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be.
  • the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.
  • a host / dopant system may be used. The principle is that when a small amount of a dopant having an energy band gap smaller than that of a host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.
  • a material forming the organic material layer in the device such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material.
  • a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.
  • Embodiments of the present invention to solve the problems of the above-described background, a compound having a thiantrene structure having a novel structure has been found, and when the compound is applied to an organic electric device, the luminous efficiency, stability and It has been found that the lifespan can be greatly improved.
  • an object of the present invention is to provide a compound having a novel thianthrene structure, an organic electric device using the same, and a terminal thereof.
  • the present invention provides a compound of the formula
  • the present invention provides a compound of the formula
  • the present invention is useful as a hole injection material, a hole transport material, a light emitting material and / or an electron transport material suitable for fluorescence and phosphorescent devices of all colors, such as red, green, blue, white, etc., depending on the compound having a thianthrene structure, It is useful as a host material for colored phosphorescent dopants.
  • the present invention also provides an organic electronic device using the compound having the above formula and a terminal including the organic electronic device.
  • Compounds having a thianthrene structure may play various roles in organic electric devices and terminals, and may be hole injection materials, hole transport materials, light emitting materials, and / or suitable for fluorescent and phosphorescent devices of all colors such as red, green, blue, and white. Or as an electron transport material, preferably as a host material for phosphorescent dopants of various colors.
  • 1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.
  • the present invention provides a compound of Formula 1 below.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol Groups, substituted or unsubstituted C1-C50 alkyl groups, substituted or unsubstituted C1-C50 alkoxy groups, substituted or unsubstituted C1-C50 alkenyl groups, substituted or unsubstituted C5-C60 arylene groups , Substituted or unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon ( At least one substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one of sulfur (
  • L is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon number 5 to 60 arylene groups, substituted or unsubstituted aryl groups having 5 to 60 carbon atoms, substituted or unsubstituted aryloxy groups having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one of (P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) At least one substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms or at least one containing sulfur
  • (3) X may have nitrogen (NR a ), oxygen (O), sulfur (S), phosphorus (PR b ), silicon (SiR c R d ) or germanium (GeR e R f ), and R a , R b , R c , R d , R e and R f are each independently an alkyl group having 1 to 60 carbon atoms or an aryl group having 6 to 60 carbon atoms.
  • R 1 and R 2 , R 3 and R 4 , R 4 and R 5 , R 5 and R 6 , R 7 and R 8 , R 8 and R 9 and R 9 and R 10 combine with adjacent groups to saturate Or unsaturated cyclic rings.
  • n is an integer of 1-3.
  • the compound having the structural formula (1) may have a symmetrical or asymmetrical structure around L.
  • the compound having the structural formula (1) can be used in a soluble process.
  • the present invention provides a compound of Formula 2 below.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted C 1-50 Alkyl group, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, substituted or unsubstituted arylene group having 5 to 60 carbon atoms, substituted or unsubstituted aryl having 5 to 60 carbon atoms Substituted or unsubstituted containing at least one group, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Substituted or unsubstituted heteroaryl having 5 to 60 carbon
  • Ar 1 and Ar 2 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted carbon group having 5 to 60 carbon atoms A substituted or unsubstituted C1-C50 alkyl group or sulfur (S) containing at least one or more of an aryloxy group, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) ), A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms or at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) or sulfur (S), nitrogen (N) , A substituted or unsubstituted heteroaryloxy group having 5 to 60 carbon atoms containing at least one of oxygen (O), phosphorus (P) and silicon (Si).
  • L is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon number 5 to 60 arylene groups, substituted or unsubstituted aryl groups having 5 to 60 carbon atoms, substituted or unsubstituted aryloxy groups having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one of (P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) At least one substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms or at least one containing sulfur
  • R 1 and R 2 and R 11 and R 12 may combine with adjacent groups to form a saturated or unsaturated cyclic ring.
  • X may have nitrogen (NR a ), oxygen (O), sulfur (S), phosphorus (PR b ), silicon (SiR c R d ) or germanium (GeR e R f ), and R a , R b , R c , R d , R e and R f are each independently an alkyl group having 1 to 60 carbon atoms or an aryl group having 6 to 60 carbon atoms.
  • n is an integer of 1-3.
  • the compound having the structural formula (2) may have a symmetrical or asymmetrical structure around L.
  • the compound having the structural formula (II) can be used in a soluble process.
  • organic electric devices exist in which compounds having a thianthrene structure described with reference to Chemical Formulas 1 to 3 are used as the organic material layer.
  • organic electroluminescent device in which the compounds having a thianthrene structure described with reference to Chemical Formulas 1 to 3 may be used include, for example, an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor (organic). TFT), photodiode, organic laser, laser diode and the like.
  • organic electroluminescent device As an example of the organic electroluminescent device (OLED) to which the compound having a thianthrene structure described above with reference to Formulas 1 to 3 can be applied, the present invention is not limited thereto, and the organic electroluminescent device is not limited thereto. Compounds having the described thianthrene structure can be applied.
  • Another embodiment of the present invention is an organic electric device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer of the organic electric field comprising the compounds of Formulas 1 to 3 Provided is a light emitting device.
  • 1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.
  • At least one layer of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer is formed to include the compounds of Formulas 1 to 3 above. Except for the above, it may be manufactured in a structure known in the art using conventional manufacturing methods and materials in the art.
  • FIGS. 1 to 6 The structure of the organic light emitting display device according to another embodiment of the present invention is illustrated in FIGS. 1 to 6, but is not limited thereto.
  • reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode.
  • the organic light emitting diode may further include a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for preventing the movement of electrons, and a protective layer.
  • the protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.
  • the compound having a thianthrene structure described with reference to Chemical Formulas 1 to 3 may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.
  • the compound having a thianthrene structure described with reference to Chemical Formulas 1 to 3 may be used instead of one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, and a protective layer. It may be used or may be used in conjunction with them to form a layer.
  • the organic layer may be used not only in one layer but also in two or more layers.
  • hole injection materials, hole transport materials, light emitting materials and / or electrons suitable for fluorescence and phosphorescent devices of all colors, such as red, green, blue, and white, according to the compound having a thianthrene structure described with reference to Chemical Formulas 1 to 3 It is useful as a transport material, as a host material for phosphorescent dopants of various colors, and especially as a green phosphorescent host material.
  • the organic light emitting device is a metal having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation
  • PVD physical vapor deposition
  • An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon.
  • PVD physical vapor deposition
  • an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
  • the organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure.
  • the organic material layer may be formed by using a variety of polymer materials, and by using a process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than a deposition method. It can be prepared in layers.
  • the organic electroluminescent device may form an organic material layer, for example, a light emitting layer, by a soluble process of a compound having a thianthrene structure described above.
  • the substrate is a support of the organic light emitting device, and a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet, or the like can be used.
  • An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon.
  • the anode material a material having a large work function is usually preferred to facilitate hole injection into the organic material layer.
  • the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the hole injection layer is located on the anode.
  • the conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.
  • the hole injection material is a material capable of well injecting holes from the anode at low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
  • the hole transport layer is positioned on the hole injection layer.
  • the hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons.
  • Tg glass transition temperature
  • Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compound, a silicon-based arylamine compound, and the like.
  • the organic light emitting layer is positioned on the hole transport layer.
  • the organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency.
  • the light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.
  • Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenol lithium salt), bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 ') to increase blue light emission efficiency.
  • an organic light emitting layer is formed of a polymer of polyphenylene vinylene (PPV) or a polymer such as poly fluorene.
  • PPV polyphenylene vinylene
  • a polymer such as poly fluorene can be used for
  • the electron transport layer is positioned on the organic light emitting layer.
  • the electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons. Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
  • the electron injection layer is stacked on the electron transport layer.
  • the electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular weight material containing boron compounds and the like.
  • the electron injection layer may be formed in a thickness range of 100 ⁇ 300 ⁇ .
  • the cathode is positioned on the electron injection layer. This cathode serves to inject electrons.
  • the material used as the cathode it is possible to use the material used for the anode, and a metal having a low work function is more preferable for efficient electron injection.
  • a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used.
  • an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 ⁇ m or less may also be used.
  • the organic light emitting device may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.
  • the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device.
  • This terminal means a current or future wired or wireless communication terminal.
  • the terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.
  • step 1) The intermediate A obtained in step 1) was dissolved in carbon tetrachloride, the reaction temperature was lowered to 15 ° C., bromine was slowly added dropwise, and the reaction was stirred at 0 ° C. for 3 hours. Water was added to terminate the reaction, and the organic layer was washed with Brine. After filtration, the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate B (yield: 92%).
  • the intermediate B obtained in step 2) was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n- BuLi (1.6 M in Hexane) was slowly added dropwise, and the reaction was stirred at 0 ° C for 1 hour. Then, the temperature of the reaction was lowered to -78 °C, Trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. Upon completion of the reaction, 2N HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with Ether. A small amount of water was removed with anhydrous MgSO 4 , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate C (yield: 77%).
  • the intermediate C and Pd (PPh 3 ) 4 , K 2 CO 3 obtained in step 3) were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 , and washed with water. A small amount of water was removed with anhydrous MgSO 4 , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate D (yield: 81%).
  • the intermediate F, Phenylboronic acid, Pd (PPh 3 ) 4 , and K 2 CO 3 obtained in step 6) were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 , and washed with water. A small amount of water was removed with anhydrous MgSO 4 , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired compound 16 (yield: 72%).
  • CuPc copper phthalocyanine
  • a-NPD 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl
  • tris (2-phenylpyridine) iridium (abbreviated as I r (ppy) 3 hereinafter) was added as a phosphorescent Ir metal complex dopant.
  • concentration of I r (ppy) 3 in the light emitting layer was 5% by weight.
  • (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolinoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a hole blocking layer to a thickness of 10 nm.
  • Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq 3 ) was formed into an electron injection layer to a thickness of 40 nm.
  • LiF an alkali metal halide
  • Al was deposited to a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic light emitting device.
  • an organic electroluminescent device having the same structure as the test example was manufactured using a compound represented by Chemical Formula 4 (hereinafter abbreviated as CBP) as a light emitting host material instead of the compound of the present invention.
  • CBP Chemical Formula 4
  • the organic electroluminescent device using the organic electroluminescent device material of the present invention is not only high efficiency and color purity, but also a long life green light emission is obtained green phosphorescent host material of the organic light emitting device It can be used to significantly improve the luminous efficiency and lifetime.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un composé présentant une structure thianthrène, un dispositif organique émettant de la lumière et un terminal comprenant ledit dispositif.
PCT/KR2010/005245 2009-08-18 2010-08-10 Composé présentant une structure thianthrène, dispositif organique émettant de la lumière et terminal comprenant ledit dispositif Ceased WO2011021803A2 (fr)

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KR10-2009-0076278 2009-08-18
KR1020090076278A KR101115036B1 (ko) 2009-08-18 2009-08-18 티안트렌 구조를 가지는 화합물 및 이를 이용한 유기전기소자, 그 단말

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WO2025110442A1 (fr) * 2023-11-20 2025-05-30 에스에프씨 주식회사 Nouveau composé hétérocyclique et diode électroluminescente organique le comprenant

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