WO2005064702A1 - An organic/macromolecular light emitting diode - Google Patents
An organic/macromolecular light emitting diode Download PDFInfo
- Publication number
- WO2005064702A1 WO2005064702A1 PCT/CN2004/001417 CN2004001417W WO2005064702A1 WO 2005064702 A1 WO2005064702 A1 WO 2005064702A1 CN 2004001417 W CN2004001417 W CN 2004001417W WO 2005064702 A1 WO2005064702 A1 WO 2005064702A1
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- WO
- WIPO (PCT)
- Prior art keywords
- group
- light emitting
- light
- layer
- emitting diode
- Prior art date
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- 239000012279 sodium borohydride Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
Definitions
- the present invention relates to a photovoltaic device, and in particular, a light-emitting diode having a extinguished light using a conjugated polymer containing a strong polar component of a polar group or an ionic group as an electron injection layer.
- Conjugated polymers are a class of polymers with large ⁇ bonds along the ⁇ ⁇ chain.
- the main chain of a conjugated polymer is generally composed of C "C single and double bonds alternately connected, the polymerization unit is 01.
- the electronic orbital of the carbon atom is sp 2 hybrid, and the three coplanar angles formed It is a 120 ° hybrid orbit.
- the Peng orbital is bonded to the adjacent carbon atom orbital to form a planar polyacetylene frame.
- the remaining unbonded P orbitals are perpendicular to this plane, and they overlap each other to form a common coordinator.
- the yoke system is similar to the one-dimensional alkali metal system. According to the calculations of ⁇ and quantum theory, when the chain length of trans polyacetylene is larger than 8 carbon atoms, it has electronic conductivity, but this kind of long The yoke system is unstable, and the Peierls phase transition will cause the energy band to split.
- the original P electrons form two subbands, namely the bond ⁇ orbital constitutes the valence band, the antibond ⁇ 3 ⁇ 43 ⁇ 4 channel constitutes the conduction band, and the bond and antibond.
- the band gap formed by the energy gap between the orbitals.
- Conductive polymers Due to the strong delocalization of electrons, stable excited and freely migrating carriers can be generated, which makes the conjugated polymer exhibit conductive properties.
- Conductive polymers also have Phases of inorganic materials for the same or similar applications , Has the advantages of low density, easy processing, wide range of synthesis options, etc. Due to the conjugate nature of this kind of material structure, it can transfer charges and be excited by light, so that it can or may be used in many electronic or optoelectronic devices, For example, high-intensity light-emitting diodes (PLEDs), photodiodes, field-effect transistors (FETs), etc. Potential application prospects and a wide range of applications have prompted scientists to compete to study such conjugate materials with optoelectronic activity.
- PLEDs high-intensity light-emitting diodes
- FETs field-effect transistors
- High ⁇ f with aromatic ring or heterocyclic structure is usually Who absorbs 300 "600 nanometers of photons and releases the corresponding energy when they form a key orbit from the anti-bond orbit.
- photons of the corresponding wavelength in the visible region are emitted, which is the electroluminescence process of high- ⁇ T materials.
- the light-emitting process of this type of electroluminescent device injects holes and electrons from the positive and negative electrodes into the light-emitting layer, and the hole-electron pair is electrically transferred in the polymer layer and captured each other to form an electrically neutral
- the bound excited state is the exciton state, and the radiation of the exciton emits a corresponding photon.
- the electroluminescence process of the high-emitting materials includes the formation of exciton and the decay of the exciton.
- the former includes the injection of carriers, the transport of carriers, and the mutual trapping shape of the carriers.
- the latter includes competition between radiation and emission processes.
- S 0
- the intersystem string ® from the triplet to the singlet state is almost impossible, so the spin is allowed to govern Luminescence (fluorescence) comes only from the singlet state.
- the first condition is to have an efficient and balanced carrier injection and.
- the simplest structure of the existing organic conjugated polymer light-emitting diode is a single-layer sandwich type, as shown in FIG. 1, which is composed of a cathode 1, a light-emitting layer 2, a hole injection layer 3, an anode 4, and a substrate 5 in order.
- a cathode 1 barium / aluminum metal is used for the cathode
- a conjugated polymer film is used for the light-emitting layer
- a PEDOT film is used for the hole injection layer
- an indium tin oxide conductive layer is used for the anode
- a glass is used for the substrate.
- the anode one uses indium tin oxide (IT0), which is transparent to visible light and has a high work function, as the electrode material, and the spin-coated high polymer ⁇ 3 ⁇ 4 material PEDOT layer is used as the electrode layer.
- I0 indium tin oxide
- PEDOT spin-coated high polymer ⁇ 3 ⁇ 4 material
- the cathode one Use low work function alkali metals (eg, potassium, lithium, cesium) or alkaline earth metals (eg, calcium, barium, etc.).
- the barrier height of electron injection (equal to the difference between the LIM0 level of the conjugated polymer material and the Fermi level of aluminum) is much higher than the potential height of the hole injection (equal to the conjugated polymer material) Difference between the HC 0 energy level and the Fermi level of indium tin oxide), and its teleportation hole mobility is much lower, in this case, the application of stable metals in the production of high-performance electroluminescent devices is greatly limited .
- lithium fluoride, etc. or surfactants have excellent effects in combination with aluminum, but they are much less effective for other metals with higher work functions.
- the electrode stabilizes the metal element to realize the electron injection of the light emitting diode.
- the purpose of the present invention is to provide a m / polymer light-emitting diode, and use a conjugated polymer containing a polar group or an ionic group of a strongly polar component as its electron injection layer.
- the yoke polymer has excellent electron injection characteristics, and the obtained L / high light emitting diode has high quantum efficiency.
- the object of the present invention is also to provide a high-molecular light-emitting diode, using a conjugated polymer containing a strong polar component containing a polar group or an ionic group as its electron injection layer.
- High work function metal which has the same or more quantum efficiency as the low work function pull-in electrode, has long-term stability and has a light emitting diode, which is suitable for high flat display.
- the a / high light emitting diode of the present invention is composed of a cathode, a light emitting diode, an anode, and a substrate, and is characterized in that a hole injection layer (3) is provided between the light emitting layer (2) and the anode (4).
- An electron injection layer (6) is provided between the cathode (1) and the light emitting layer (2), and the electron injection layer uses a polar unit conjugated polymer containing a polar group or an ionic group.
- the light-emitting layer (2) and the electron injection layer (6) can also be combined into one layer, and this layer is a hair emission at the same time;) fc and the electron injection layer adopt polar units containing polar groups or ionic groups Conjugated polymers.
- the organic / polymer light emitting diode of the present invention has m / high light emission, which is formed by stacking a cathode 1, a light emitting layer 2, a hole injection layer 3, an anode 4, and a substrate 5 in this order.
- an electron 3 ⁇ 4 layer 6 is provided between the cathode and the light-emitting layer.
- the 3 ⁇ 4 electron injection layer uses a conjugated polymer of a polar unit containing a polar group or an ionic group.
- a conjugated polymer containing a polar unit of a polar group or an ionic group has the following structure:
- A is a polar component containing a polar group or an ionic group, and has a combination of one or more of the following structures:
- the components of the ionic group have one or more of the following structures ⁇
- G is a heterocyclic ring that may contain sulfur, nitrogen, and selenium, such as benzothiadiazole, benzoseladiazole;
- a conjugated polymer containing polar units containing polar groups or ionic groups can be obtained by coupling reactions of ⁇ ⁇ to Mil Suzuki.
- the cathode metal may be a low work function metal or a high work function metal.
- ⁇ m / high light-emitting diodes In order to overcome the low work function metal's easy reaction with water and oxygen, which causes rapid aging and failure of the device, and the processing difficulties caused by iWd, and to overcome the low electron injection efficiency of high work function metal, ⁇ m / high light-emitting diodes During the process, a solution of the above polar group or ionic group polymer is rotated, and a thin layer is coated on the light-emitting layer to form an electron injection layer, and then a high-efficiency metal is plated thereon. Get good environmental stability! Efficient! Balanced electrons are injected into the light emitting diode.
- the high work function metals are gold, aluminum, copper, silver, indium, nickel, lead, tin, carbon, graphite, or alloys thereof.
- the light-emitting layer can be a light-emitting layer commonly used in the prior art, or a copolymer of 3 ⁇ 4-inch benzene, polyfluorene, poly SPIR0 "p-benzene, ladderfPP, and phenylene acetylene substituted with a light-emitting group.
- the copolymers synthesized by the present invention can achieve excellent electron injection to red, green and blue light emitting materials regardless of any band gap width.
- the electrons are not affected by the work function of the yin face, even if it is a ⁇ stable metal with a work function up to 5.2eV
- a light-emitting device with high quantum efficiency and long-term stability can be obtained similarly to the low-work-function injection electrode, which is suitable for high-flat displays.
- This kind of materials with polar groups can be dissolved in water or methanol. Since the light emitting materials are generally insoluble, no mixing phenomenon will occur between the electron injection layer and the light emitting layer when constructing a multilayer device.
- High work function metals have excellent air 3 ⁇ 4 ⁇ vapor stability.
- the composite electrode composed of the polymer and the high work function metal of the present invention has stable processing performance in the atmosphere, and the stability of the device itself is greatly improved. Huge potential area in organic and high-quality display technology
- Figure 1 is a schematic diagram of the structure of an existing organic conjugated polymer light emitting diode
- FIG. 2 is an energy band diagram of a device using aluminum as a cathode
- FIG. 3 is a schematic structural diagram of a light emitting diode with an iy height of the present invention
- Figure 4 compares the presence or absence of a P1 layer when poly [2-methoxy (5- (2, monoethyl) -B3 ⁇ 4 «-l, 4-phenylacetylene)] (MEH-PPV) material is used as a cathode Curve of luminous brightness and external quantum efficiency of the device;
- Fig. 5 is a graph comparing the luminous brightness and the external quantum efficiency curve of a device emitting green light benzene S3 ⁇ 4-generation poly-p-phenylacetylene (P-PPV) and a device with or without a PI layer when gold is used as a cathode;
- P-PPV green light benzene S3 ⁇ 4-generation poly-p-phenylacetylene
- FIG. 6 is a graph comparing the luminous brightness and the luminous external quantum efficiency of a device with or without a PI layer when using gold as a cathode for a blue-emitting Poly Wat Pro;
- Fig. 7 is a graph showing the luminous brightness and the external light emitting quantum efficiency of the device with or without the P1 layer when the red-emitting ffl-PPV uses aluminum as a cathode in Fig. 7;
- 2,7-Dibromofluorene was prepared according to the method disclosed in the 1997 world patent WO 99 05184 and disclosed in "Chem. Mater” 11 (1997) 11083.
- Example 2 Preparation of 2,7-dibromo "9, 9 ⁇ di-substituted hydride replacement sheet (Article 26 of the detailed rules) Take the preparation of 2,7-dibromo ", ⁇ dizhenzahuhu as an example. According to the method disclosed in the 1997 world patent TO 99 05184 and the" Chem Mater "11 (1997) 11083, the process 2 , 7-dibromo ⁇ 9, 9 ⁇ di-n-octyl hydrazone.
- the 2,7-dibromo-9,9 "di-substituted substituents include, but are not limited to, n-hexyl, n-octyl, 2-ethyl beta, decyl, and the like.
- Example 3 Preparation of 3, 6 "" dibromocarbazole
- Dibromo-N-substituted yttriazoles include: n-hexyl, n-octyl, 2-ethylhexyl, etc., but is not limited thereto.
- Example 5 Preparation of 9, 9 ⁇ disubstituted-2,7-diborate hydrazone
- the substituents in 9, 9 ⁇ disubstituted -2, 7-diborate hydrazone include: n-hexyl, n-hexyl, 2-ethylhexyl, decyl, but not limited thereto.
- Substitution-3, Substitution in carbazole 3 ⁇ 4 ⁇ include: but not limited to n-hexyl, n-octyl, 2-ethylhexyl and the like.
- Example 7 Preparation of dibromo group at side 9 with amine-containing functional group side chain
- Substituents in 2,7-dibromo ⁇ , 9 "di-B3 ⁇ 4" substitutions include: ⁇ , ⁇ dimethylaminopropyl, ⁇ , ⁇ -dimethylaminoethyl, ⁇ , "dimethylaminohexyl, N ⁇ ethylaminoethyl and the like are not limited thereto.
- Example 8 Preparation of dibromo group at the 9-position with a sulfonic acid group-containing functional side chain
- the substituents in 2,7-dibromo ⁇ 9, 9 ⁇ disulfonium include: sulfopropyl, potassium sulfopropyl, sulfobutyl, potassium sulfonate and the like, but are not limited thereto.
- the pendant substituents of the dibromocarbazole containing a sulfonic acid functional group side chain include: sulfopropyl, potassium sulfopropyl, sodium sulfonate butyl, potassium sulfonate, but are not limited thereto.
- Example 11 Preparation of p-dibromobenzene with a side chain containing an amine-containing functional group
- Substitute page (rule 26) Take the preparation of 2,5-bis (3- [N, ⁇ diethylamino] -1-oxopropyl-1,4-dibromobenzene as an example. Press "Macromolecules" 30 (1997 ) The method disclosed in 7686 is used to prepare 2, 5-bis (3- [N, diethyl 3 ⁇ 43 ⁇ 4] -1-oxopropane S ⁇ l, 4-dibromobenzene.
- the side chain with amine group in p-dibromobenzene with side chain containing amine functional group includes N, dimethylaminopropyl, ⁇ , ⁇ -dimethylaminoethyl, ⁇ , N-dimethylaminohexyl, N, ⁇ diethylaminoethyl, and the like, but are not limited thereto.
- Example 12 Preparation of 4, 7-dibromo-2,1,3-benzoselenediazole according to the method and method disclosed in J. Chem. Soc. (1963) 4767. 7-dibromo-2,1,3-benzoselenediazole. Weigh 2,1,3-benzoselenediazole (1.83 g, 0.01 mole) and silver sulfate (3.12 g, 0.01 mole), dissolve in 20 ml of concentrated sulfuric acid, stir, and add bromine (3.2 g, 0.02 mole) dropwise.
- ITO conductive glass square resistance ⁇ 20 ⁇ / port, pre-cut into 15 mm X 15 mm square pieces.
- IT0 nets were bombarded with plasma in an oxygen plasma etcher for 10 minutes.
- PVK, PED0T: PSSPVK were purchased from Aldrich, and the solution was prepared with tetrachloroethane.
- PED0T PSS water dispersion (about 1%) was purchased from Bayer's buffer layer and spin-coated with a homogenizer (KW-4A). The thickness was determined by the solution concentration and speed.
- a surface profiler Tritek Alpha-Tencor500 was used. ) Measured monitoring. After film formation, the solvent residue and hard film were driven out in a constant temperature vacuum oven.
- the fluorescent conjugated polymer was weighed in a clean bottle, it was transferred to a nitrogen-resistant film-forming glove box (VAC company), dissolved in toluene, and filtered through a 0.45 micron filter membrane.
- the optimal thickness of the polymer light-emitting layer is 70 to 90 nm.
- the film thickness was measured with a TENCORALFA-STEP-500 surface profiler.
- P1 was dissolved in methanol (a small amount of acetic acid was added) to prepare a 0.04% 0. two concentration solution. Profit
- a 90-nm-thick poly [2-methoxy (5- (2, monoethyl) -hexadecane-1,4-phenyleneacetylene]] (MEtt-PPV) conjugated polymer film was used as the light-emitting layer.
- A1 Function of A1 (44 electron volts), Au (5.3 electron volts), alternating at different concentrations (2, 5-bis (3- [N, F "diethylamino] 1-oxypropyl 3 ⁇ 4 ⁇ 1, 4 —Benzene—co- ⁇
- a thin layer of P1 is spin-coated under a methanol solution of 9 "di-copolymer (P1) in a light-emitting layer; ⁇ as an electron injection layer, vacuum-evaporated over the electron injection layer P1 covered with aluminum
- a double-layered structure of gold or gold is used as a cathode to produce a polymer light emitting diode emitting orange-red light.
- a low work function Ba (2.7 electron volts) / A1 and a high work function are used.
- the conventional light-emitting device prepared by directly vapor-depositing Al (4.2 electron volts) and Au (5.3 electron volts) on 3 ⁇ 4 MEHPPV was used as a reference device, and the measurement results are shown in Table 1.
- the comparative poly [2— Methoxy (5- (2, monoethyl) -hexyloxy-1,4-phenylethyl block)] (MEH-PPV) material, with or without P1 layer when using aluminum as cathode The device's luminous effect shines outside quantum efficiency.
- MEHPPV Pl (0.0%) aluminum 7.0 24.7 2247 229
- Table 2 is based on the 3 ⁇ 43 ⁇ 43 ⁇ 43 ⁇ 4 performance of the device using PI as the electronic layer for the material P "PPV, and the device structure is ITO ⁇ EDOT / ADS129 / Al (Au) m electron 3 ⁇ 4 ⁇ cathode mt. External quantum efficiency fiber (Amp. Square meter) eo )
- Example 2 to replace the polymer light-emitting layer with; 3 ⁇ 4 light Pho material PFO, spin-coated a 40nm PW layer on the layer, to improve the injection of holes, the others remain unchanged.
- the experimental results are summarized in Table 3.
- the light-emitting poly PF0 uses the gold as the cathode and the light emission of the device with or without the P1 layer 3 ⁇ 4 3 ⁇ 4 3 ⁇ 4 Quantum efficiency.
- Table 3 shows the electrical properties of the device using PP1 as the electron 3 ⁇ 4 ⁇ layer.
- the device structure is ITO PEDOT P ADS ⁇ g / Pl / Al (Au)
- Example 2 was repeated.
- the electron injection layer was replaced with a polymer (P2) having a sulfo 3 ⁇ 4 group functional group in the side chain, and the others were unchanged.
- P2 polymer having a sulfo 3 ⁇ 4 group functional group in the side chain
- Table 4 The experimental results are summarized in Table 4.
- Figure 7 when the red-emitting MEH-PPV uses aluminum as the cathode, the light emission brightness and external light emission quantum efficiency of the device with or without the P1 layer are compared.
- Example 2 was repeated.
- the electron injection layer was replaced with a three-component copolymer containing a narrow band gap (narrow band gap monomer benzothiadi (P3) as the electron injection layer.
- the other cakes were unchanged.
- the experimental results are summarized in Table 5.
- Table 5 Based on the red light material poly [2-methoxy (5- (2, monoethyl) -hexyloxy-1, 4-phenylphenylacetylene)] (Mffi-PPV), with a narrow band gap monomer benzothia
- the ternary copolymer of a diazole e.g., the electroluminescence properties of a device as an electric layer
- the device structure is ITO / PEDOT / MEHPPV / P3 / A1 m electrons, cathode voltage, current, and efficiency.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Electroluminescent Light Sources (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The present invention relates to an organic/macromolecular light emitting diode, which is composed of cathode (1), light emitting layer (2), hole-injecting layer (3) anode (4) and substrate (5) by sequentially laminating. A electron-injecting layer (6) is provided between the cathode (1) and the light emitting layer (2), the said electron-injecting layer adopts the conjugated polymer which contains polarity unit of polarity group or ionicity group; the said cathode adopts high work-function metal that the workfunction is greater than or equal to 3.6eV. The present invention can obtain the organic/macromolecular light emitting diode that it has the same or higher quantum efficiency of low work-functional as the injecting electrode, its longtime stability becomes better, the organic/macromolecular light emitting diode is fit for the full-colored & fine resolution flat panel display device.
Description
有机厳子发光二极管 技术领域 TECHNICAL FIELD
本发明涉及光电器件， 特别是用含有极性基团或离子性基团的强极性组分的共轭聚合物作为电 子注入层的有滅好发光二极管。 The present invention relates to a photovoltaic device, and in particular, a light-emitting diode having a extinguished light using a conjugated polymer containing a strong polar component of a polar group or an ionic group as an electron injection layer.
背景技术 Background technique
自 1977年日本科学家白川英树发现聚乙炔导电以来， 这种被称为 "***髙分子"材料的共轭 聚合物以其突出的光电性能吸弓 I了众多科学家进行研究。共轭聚合物是一类沿着^ ΐ链有大 π键的 聚合物。共轭聚合物的主链一般由 C"C单键和双键交替联结而成， 聚合单元是 01。其中的碳原子的 电子轨 取的是 sp2杂化， 形成的三个共平面夹角是 120° 的杂化轨道。鹏轨道与相邻的碳原子 轨道键合构成平面型的聚乙炔框架， 剩下的未成键 P轨道与这一平面相垂直， 它们互相重叠， 形成 呈的 ^共轭体系，类似于一维的碱金属体系。根据^ ^学和量子学的计算，当反式聚乙炔的大 ^ m \ 8个以上碳原子链长时即具有电子导电性， 但是这种长 轭体系不稳定， 会发生 Peierls 相变导致能带***， 是原有的 P电子形成两个亚带， 即成键 π轨道构成价带， 反键 π¾¾道构成的 导带以及成键与反键轨道间的能隙构成的禁带。 由于^电子的离域化较强， 因而可以产生稳定的激 发、 自由迁徙的载流子， 使得共轭聚合物表现出导电的特性。 导电高分子同具有相同或相近用途的 无机材料相比， 具有密度低， 易于加工， 合成选择范围广等优点。 由于这类材料结构的共轭特性， 使它能传输电荷， 受激发光， 从而能够或潜在可能在许多电子或光电子器件上得到应用， 例如包括 高^ Τ发光二极管 (PLEDs) ,光电二极管，场效应管 (FET)等。潜在的应用前景和广泛的应用领域促使 科学家竞相研究这类具有光电活性的共轭材料， 巳经为世人所熟知的包括聚乙炔，聚吡咯，聚噻吩， 聚苯胺， 聚苯撑乙炔， 聚笏等。 当电子从成键轨 反键轨道时 - 膨， 带有芳环或杂 环结构的高^ f通常吸誰长 300"600纳米的光子，当从反键轨 成键轨道时，释放出相应的 能量， 通常发出可见区内相应波长的光子， 就是^；高^ T材料的电致发光过程。 Since the Japanese scientist Hideki Shirakawa discovered that polyacetylene is conductive in 1977, this conjugated polymer, known as the "fourth-generation fluorene molecule," has attracted many scientists for its outstanding photoelectric properties. Conjugated polymers are a class of polymers with large π bonds along the ^ ΐ chain. The main chain of a conjugated polymer is generally composed of C "C single and double bonds alternately connected, the polymerization unit is 01. The electronic orbital of the carbon atom is sp 2 hybrid, and the three coplanar angles formed It is a 120 ° hybrid orbit. The Peng orbital is bonded to the adjacent carbon atom orbital to form a planar polyacetylene frame. The remaining unbonded P orbitals are perpendicular to this plane, and they overlap each other to form a common coordinator. The yoke system is similar to the one-dimensional alkali metal system. According to the calculations of ^^^ and quantum theory, when the chain length of trans polyacetylene is larger than 8 carbon atoms, it has electronic conductivity, but this kind of long The yoke system is unstable, and the Peierls phase transition will cause the energy band to split. The original P electrons form two subbands, namely the bond π orbital constitutes the valence band, the antibond π¾¾ channel constitutes the conduction band, and the bond and antibond. The band gap formed by the energy gap between the orbitals. Due to the strong delocalization of electrons, stable excited and freely migrating carriers can be generated, which makes the conjugated polymer exhibit conductive properties. Conductive polymers also have Phases of inorganic materials for the same or similar applications , Has the advantages of low density, easy processing, wide range of synthesis options, etc. Due to the conjugate nature of this kind of material structure, it can transfer charges and be excited by light, so that it can or may be used in many electronic or optoelectronic devices, For example, high-intensity light-emitting diodes (PLEDs), photodiodes, field-effect transistors (FETs), etc. Potential application prospects and a wide range of applications have prompted scientists to compete to study such conjugate materials with optoelectronic activity. Well-known include polyacetylene, polypyrrole, polythiophene, polyaniline, polyphenylene acetylene, poly Watt, etc. When the electrons from the bond orbital to the antibond orbital-swell, high ^ f with aromatic ring or heterocyclic structure is usually Who absorbs 300 "600 nanometers of photons and releases the corresponding energy when they form a key orbit from the anti-bond orbit. Usually, photons of the corresponding wavelength in the visible region are emitted, which is the electroluminescence process of high- ^ T materials.
由于发光高^ ^器件具有材料成本低廉， 易于大面积成型， 驱动电压低， 能耗小， 发光波长可 替换页（细则第 26条）
材料结构调谐等突出优点， ί ^了信息显示技术的一场革命。在过去的+^里， 各国科学家开 发了数量众多的发光聚合物。这类电致发光器件的发光过程是在外加电场作用下， 由正， 负电极向 发光层注入空穴与电子， 空穴一电子对在聚合物层 电 移， 互相俘获， 形成电中性的束缚 激发态即激子态， 激子的辐射 发出相应的光子。 由此可见， 发光高 ^材料的电致发光过程包 括激子的形成和激子的衰退， 前者包括载流子的注入， 载流子的输运以及薪流子的互相俘获形 « 子。后者包括辐射过程和離射过程的竞争。 由于激子包括两个自旋为 1/2的带电粒子， 所以其自 旋波函数是单重态 (S=0) '或者是三重态（s=i)。作为激发受束缚的结果，激子单重态和三重态之间 的转换能很大， 这样， 从三重态到单重态的系间串 ®Λ乎是不可能的， 所以自旋允许辖射发光（荧 光）只来自单重态。要得到高效、稳定的电致发光器件， 首要的条件是有高效， 平衡的载流子注入 和 。 Due to the high light emitting device, the material cost is low, it is easy to form a large area, the driving voltage is low, the energy consumption is small, and the light emission wavelength can be replaced. (Article 26 of the detailed rules) Material structure tuning and other outstanding advantages have revolutionized information display technology. In the past, scientists from various countries have developed a large number of light-emitting polymers. Under the action of an external electric field, the light-emitting process of this type of electroluminescent device injects holes and electrons from the positive and negative electrodes into the light-emitting layer, and the hole-electron pair is electrically transferred in the polymer layer and captured each other to form an electrically neutral The bound excited state is the exciton state, and the radiation of the exciton emits a corresponding photon. It can be seen that the electroluminescence process of the high-emitting materials includes the formation of exciton and the decay of the exciton. The former includes the injection of carriers, the transport of carriers, and the mutual trapping shape of the carriers. The latter includes competition between radiation and emission processes. Since the exciton includes two charged particles with a spin of 1/2, its spin wave function is a singlet state (S = 0) 'or a triplet state (s = i). As a result of the excitation and restraint, the conversion between the exciton singlet state and triplet state is very large. In this way, the intersystem string ® from the triplet to the singlet state is almost impossible, so the spin is allowed to govern Luminescence (fluorescence) comes only from the singlet state. To obtain an efficient and stable electroluminescent device, the first condition is to have an efficient and balanced carrier injection and.
最简单的现有有机共轭聚合物发光二极管的结构是单层夹心式， 如图 1所示，由阴极 1、发光层 2、空穴注入层 3、 阳极 4、衬底 5依次层叠构成。一般情况下， 其中阴 用钡 /铝金属， 发光层采 用共轭聚合物薄膜， 空穴注入层采用 PED0T薄膜， 阳极采用氧化铟锡导电层， 衬底采用玻璃， 当在 阳极和阴极之间施加适当的正向偏压后就会发光。 为确保电子空穴的充分注入其中， 阳极一¾¾用 对可见光透明的、 具有高功函数的氧化铟锡 (IT0)作为电极材料， 配合旋涂高 聚^ ¾材料 PEDOT 层作为电极 ί排层， 阴极一 用低功函数的碱金属 (如， 钾， 锂， 铯） ， 或碱土金属 (如， 钙， 钡 等)。 The simplest structure of the existing organic conjugated polymer light-emitting diode is a single-layer sandwich type, as shown in FIG. 1, which is composed of a cathode 1, a light-emitting layer 2, a hole injection layer 3, an anode 4, and a substrate 5 in order. In general, barium / aluminum metal is used for the cathode, a conjugated polymer film is used for the light-emitting layer, a PEDOT film is used for the hole injection layer, an indium tin oxide conductive layer is used for the anode, and a glass is used for the substrate. When applied between the anode and the cathode It emits light after proper forward bias. In order to ensure the full injection of electrons and holes, the anode one uses indium tin oxide (IT0), which is transparent to visible light and has a high work function, as the electrode material, and the spin-coated high polymer ^ ¾ material PEDOT layer is used as the electrode layer. The cathode one Use low work function alkali metals (eg, potassium, lithium, cesium) or alkaline earth metals (eg, calcium, barium, etc.).
虽然这类低功函数的碱金属及碱土金属易与水，氧反 J3¾ 成加工的困难，器件需要严密的爐， 但是当 环境稳定性好的金属比如铝作为阴极时， 要获得稳定， 髙效， 平衡的电子注入成为一个 难于逾越的技术屏障。 这是由于大部分共轭聚合物都属 P型半导体， 其最低非占有好轨道能量 (画）较高， 以铝作为阴极的器件为例， 图 2为器件的能带图。 如图 2所示， 电子注入的势垒高 度（等于共轭聚合物材料的 LIM0能级与铝的费米能级之差）大大高于空穴注入的势皇高度（等于共 轭聚合物材料的 HC 0能级与氧化铟锡的费米能级之差)， 且其电 移報空穴迁移率低很多， 这 样的情况下， 大大限制了稳定金属在制作高性能电致发光器件的应用。 Although this kind of low work function alkali metals and alkaline earth metals are easy to be processed with water and oxygen, and the device requires a strict furnace, when a metal with good environmental stability such as aluminum is used as a cathode, it must be stable and effective. Balanced electron injection becomes a technical barrier that is difficult to cross. This is because most conjugated polymers are P-type semiconductors, and their lowest non-occupied good orbital energies (drawing) are relatively high. Taking aluminum as a cathode device as an example, Figure 2 shows the energy band diagram of the device. As shown in Figure 2, the barrier height of electron injection (equal to the difference between the LIM0 level of the conjugated polymer material and the Fermi level of aluminum) is much higher than the potential height of the hole injection (equal to the conjugated polymer material) Difference between the HC 0 energy level and the Fermi level of indium tin oxide), and its teleportation hole mobility is much lower, in this case, the application of stable metals in the production of high-performance electroluminescent devices is greatly limited .
2 2
替换页（细则第 26条)
因此在有机高 发光研究领域研究人员—直在努力开发电子注入型过渡材料， 当将薄层的这 爾料加在阴极与发光层之间时， 有效降低这类金属与发光层之间的电子注入势垒， 从而可以麵 具有较高功函数的金属作为阴极得到有效的电子注入及髙效的发光器件。在此前的技术中比较广泛 采用的是棚碱金属， 或碱土金属的卤化物， 或氧化物 (Cao' PCT) 等薄层。例如 Hung等釆用一薄层 氟化锂蒸镀于有机小 发光材料如 alq3 ; ±。在氟化锂层之上再蒸鍍铝金属电极，这样所组成的 LiF/Al复合阴极可以得到高效的发光器件。 同样用氟化锂等蒸镀在聚合物发光材料上也可得到同样 的效果， 美国专利 USPatot5^65^81 (1999){細一种具有表面活性剂 的小 有机 用溶液成 膜的方式涂敷于有机或高^ 1发光层上， 上面再镀上金属铝， 也可以得到效率极高的发光器件。但 这类现有的技术方法都有一个共同的缺陷， 只对某赚定的金属有辙子的效果。如上述专利技术中 的氟化锂等或表面活性剂都与铝配合有极好的效果， 但对其他更高功函数的金属则效率差很多， 例 如至今 见有娜见有技术可以用金等电极稳定的金属元素来实现发光二极管的电子注入。 Replacement page (Article 26) Therefore, researchers in the field of organic high-luminescence research have been working hard to develop electron-injection transition materials. When a thin layer of this material is added between the cathode and the light-emitting layer, the electrons between the metal and the light-emitting layer are effectively reduced. A potential barrier is injected, so that a metal having a higher work function can be used as a cathode to obtain an effective electron injection and ineffective light emitting device. In previous technologies, thin layers such as halides of alkali metals, or alkaline earth metals, or oxides (Cao 'PCT) are more widely used. For example, Hung et al. Used a thin layer of lithium fluoride to deposit on small organic light-emitting materials such as alq3; ±. An aluminum metal electrode is vapor-deposited on the lithium fluoride layer, so that the composed LiF / Al composite cathode can obtain an efficient light emitting device. The same effect can also be obtained on polymer light-emitting materials by evaporation of lithium fluoride, etc. US Patent USPatot 5 ^ 65 ^ 81 (1999) {Fine coating method for a small organic solution with a surfactant ^ on the organic light-emitting layer or high, then top coated with aluminum metal, can be obtained very high efficiency light emitting device. However, this type of existing technical methods all have a common defect, which is only rude for certain metals. For example, in the above patented technology, lithium fluoride, etc. or surfactants have excellent effects in combination with aluminum, but they are much less effective for other metals with higher work functions. For example, until now, there are technologies that can use gold, etc. The electrode stabilizes the metal element to realize the electron injection of the light emitting diode.
发明内容 Summary of the invention
本发明的目的在于 共一种有 m/高分子发光二极管，用含有极性基团或离子性基团的强极性组 分的共轭聚合物作为其电子注入层，本发明樹共的共轭聚合物具有优异电子注入特性，得到的有 L/ 高 发光二极管量子效率高。 The purpose of the present invention is to provide a m / polymer light-emitting diode, and use a conjugated polymer containing a polar group or an ionic group of a strongly polar component as its electron injection layer. The yoke polymer has excellent electron injection characteristics, and the obtained L / high light emitting diode has high quantum efficiency.
本发明的目的还在于提供一种有 in高分子发光二极管，用含有极性基团或离子性基团的强极性 组分的共轭聚合物作为其电子注入层的同时， 其阴极可以采用高功函数金属， 得到与低功函撤入 电极同样或更髙量子效率，长期稳定性 的有謹 发光二极管，适用于高 平面显示 器。 The object of the present invention is also to provide a high-molecular light-emitting diode, using a conjugated polymer containing a strong polar component containing a polar group or an ionic group as its electron injection layer. High work function metal, which has the same or more quantum efficiency as the low work function pull-in electrode, has long-term stability and has a light emitting diode, which is suitable for high flat display.
本发明的有 a/高 发光二极管， 由阴极、发 ¾ 、 阳极、衬底依 叠构成， 其特点是在发 光层 (2)和阳极 (4)之间设一空穴注入层 (3)， 在阴极 (1)与发光层 (2)之间设一电子注入层 (6)， 所述电 子注入层采用含有极性基团或离子性基团的极性单元共轭聚合物。 The a / high light emitting diode of the present invention is composed of a cathode, a light emitting diode, an anode, and a substrate, and is characterized in that a hole injection layer (3) is provided between the light emitting layer (2) and the anode (4). An electron injection layer (6) is provided between the cathode (1) and the light emitting layer (2), and the electron injection layer uses a polar unit conjugated polymer containing a polar group or an ionic group.
本发明也可以将发光层 (2)与电子注入层 (6)合并为一层，该层同时是发;) fc 和电子注入层，采用 含有极性基团或离子性基团的极性单元共轭聚合物。 In the present invention, the light-emitting layer (2) and the electron injection layer (6) can also be combined into one layer, and this layer is a hair emission at the same time;) fc and the electron injection layer adopt polar units containing polar groups or ionic groups Conjugated polymers.
3 3
替换页（细则第 26条）
如图 3所示， 本发明的有机 /高分子发光二极管是在现有由阴极 1、发光层 2、空穴注入层 3、阳 极 4、衬底 5依次层叠构成的有 m/高 ^^发光二极管的基础上， 在阴极与发光层之间设一电子 ¾Λ 层 6， 戶 ¾电子注入层采用含有极性基团或离子性基团的极性单元的共轭聚合物。 Replacement page (Article 26) As shown in FIG. 3, the organic / polymer light emitting diode of the present invention has m / high light emission, which is formed by stacking a cathode 1, a light emitting layer 2, a hole injection layer 3, an anode 4, and a substrate 5 in this order. On the basis of the diode, an electron ¾ layer 6 is provided between the cathode and the light-emitting layer. The ¾ electron injection layer uses a conjugated polymer of a polar unit containing a polar group or an ionic group.
戶 含有极性基团或离子性基团的极性单元的共轭聚合物， 具有如下结构：
A conjugated polymer containing a polar unit of a polar group or an ionic group has the following structure:
其中 r¾ =1, 2, 3···.；] ¾, Ώτϋ, 1,2· Where r¾ = 1, 2, 3 ··· .;] ¾, Ώτϋ, 1,2 ·
其中 Α为含有极性基团或离子性基团的极性组分， 具有如下其中一种或多种结构的组合: Wherein A is a polar component containing a polar group or an ionic group, and has a combination of one or more of the following structures:
聚芴：
其中 ， 为带有,、 安盐基、腈基、羧基、横酸基、磷酸 中一 个或多个的侧链； n=l, 2, 3
Ϊ¾， ι¾为带有藤、 m,腈基、 磺酸基、磷酸 中一个 Juying: Wherein, it is a side chain bearing one or more of, hydrazine, nitrile, carboxyl, transverse acid, and phosphoric acid; n = 1, 2, 3 Ϊ¾, ι¾ is one with vine, m, nitrile, sulfonic acid, or phosphoric acid
聚 SPIRiH (寸苯:
其中 Rl， 为带有 S錢、 安盐基、腈基、羧基、磺酸基、 磷酸鎮中一个或多个的侧链； n=l, 2, 3· Poly SPIRiH (inch benzene: Where Rl is a side chain bearing one or more of sulfanyl, sulfonyl, nitrile, carboxyl, sulfonic acid, and phosphate; n = l, 2, 3 ·
替换页（细则第 26条）
苯撑乙炔： 2 」η其中 R， ！¾为带有胺基、 安盐基、腈基、羧基、磺酸基、磷酸基 其中一个或多个的侧链； n=l, 2, 3…… - Replacement page (Article 26) Phenylene ethynylene: 2 "η wherein R,! ¾ is a side chain having one or more of an amine group, a hydrochloride group, a nitrile group, a carboxyl group, a sulfonic acid group, and a phosphate group; n = 1, 2, 3 ...-
聚咔唑：
Rl为带有胺基、 安盐基、 fl青基、羧基、磺酸基、磷酸 中一水 或多个的侧链； n=l, 2， 3…… · 其中 B为不含有极性或离子性基团的组分， 具有如下的一种或几种结构- Polycarbazole: Rl is a side chain having one or more of amine group, hydrazine group, flenyl group, carboxyl group, sulfonic group, and phosphoric acid; n = 1, 2, 3 ... The components of the ionic group have one or more of the following structures −
辦 Do
舰 Ship
聚 SPI 3- Poly SPI 3-
»苯
撑乙炔： 2, 3· "benzene Acetylene: 2, 3 ·
聚咔唑:
为 H， 的垸基； n=l, 2, 3· Polycarbazole: Is a fluorene group of H, n = l, 2, 3 ·
其中 G为 可含有硫， 氮， 硒的杂环， 例如苯并噻二唑， 苯并硒二唑; Where G is a heterocyclic ring that may contain sulfur, nitrogen, and selenium, such as benzothiadiazole, benzoseladiazole;
5 5
替换页（细则第 26条)
以±≡种成 Mil Suzuki偶合反应即可得到含有极性基团或离子性基团的极性单元的共轭聚合 物。 Replacement page (Article 26) A conjugated polymer containing polar units containing polar groups or ionic groups can be obtained by coupling reactions of ± ≡ to Mil Suzuki.
制^ m/高 ^^发光二极管时，可以将 ±¾聚 勿的溶液 旋转， 印刷等方式在发光层上涂 敷一薄层形成电子注入层， 然后在其上再 阴极金属。所述阴极金属可以是低功函数金属、 或高 功函数金属。 When manufacturing ^ m / h ^^ LEDs, you can rotate a ± ¾ polymer solution, print, etc. on the light-emitting layer to form a thin layer to form an electron injection layer, and then cathode metal on it. The cathode metal may be a low work function metal or a high work function metal.
为了克服低功函数金属易于与水， 氧反应， 造成器件迅速老化失效， 以及由 iWd 成的加工上的 困难， 同时为了克服高功函数金属低的电子注入效率， 在制^ m/高 发光二极管的过程当中， 将上述极性基团或离子性基团聚合物的溶液逝旋转， 印刷等方式在发光层上涂敷一薄层形成电子 注入层， 然后在其上再镀上高功赚金属， 获得环境稳定性良好！ 具有高效！ 平衡的电子注入的有 w髙好发光二极管。 In order to overcome the low work function metal's easy reaction with water and oxygen, which causes rapid aging and failure of the device, and the processing difficulties caused by iWd, and to overcome the low electron injection efficiency of high work function metal, ^ m / high light-emitting diodes During the process, a solution of the above polar group or ionic group polymer is rotated, and a thin layer is coated on the light-emitting layer to form an electron injection layer, and then a high-efficiency metal is plated thereon. Get good environmental stability! Efficient! Balanced electrons are injected into the light emitting diode.
戶 ί¾高功函数金属是金， 铝， 铜， 银， 铟， 镍， 铅， 锡， 碳， 石墨， 或其合金。 The high work function metals are gold, aluminum, copper, silver, indium, nickel, lead, tin, carbon, graphite, or alloys thereof.
戶 发光层可以是现有技术通用的发光层，也可以是发光基团被取代的 ¾寸苯，聚芴,聚 SPIR0" 对苯， 梯形爾苯 (ladderfPP) , 舰苯撑乙炔的共聚物。 The light-emitting layer can be a light-emitting layer commonly used in the prior art, or a copolymer of ¾-inch benzene, polyfluorene, poly SPIR0 "p-benzene, ladderfPP, and phenylene acetylene substituted with a light-emitting group.
本发明与现有技稀匕具有如下优点： The present invention and the prior art thin dagger have the following advantages:
(1)本发明所合成的共聚合物对不论何种带隙宽度的红、绿、蓝三色发光材料者阿以实现优异 的电子注入。 (1) The copolymers synthesized by the present invention can achieve excellent electron injection to red, green and blue light emitting materials regardless of any band gap width.
(2)在与红，绿，蓝三色发光聚合物所所组成的多层器件中电子可不受阴†脸属功函数的影响， 即使^ 象^ ¾样功函数高达 5.2eV的髙稳定金属， 也可以得到与低功函数注入电极同样^ ¾高量 子效率， 长期稳定髓的发光器件， 适用于高 平面显示器。 (2) In multilayer devices composed of red, green, and blue light-emitting polymers, the electrons are not affected by the work function of the yin face, even if it is a ^ stable metal with a work function up to 5.2eV A light-emitting device with high quantum efficiency and long-term stability can be obtained similarly to the low-work-function injection electrode, which is suitable for high-flat displays.
(3)这类带有极性基团的材料可溶解于水或甲醇等极性翻中。而发光高 才料一般不溶于 因此在构筑多层器件时电子注入层与发光层之间不会发生混合现象。 (3) This kind of materials with polar groups can be dissolved in water or methanol. Since the light emitting materials are generally insoluble, no mixing phenomenon will occur between the electron injection layer and the light emitting layer when constructing a multilayer device.
(4)由于 ^^高功函数金属具有优异的空气 ¾τκ汽稳定性。 本发明所 的聚合物与高功 函数的金属所组成的复合电极雕大气中加工的稳定 f生， 器件本身的稳定性也大大提髙。在有机和 高好发光显示屏技术中巨大的潜在的麵 (4) ^^ High work function metals have excellent air ¾τκ vapor stability. The composite electrode composed of the polymer and the high work function metal of the present invention has stable processing performance in the atmosphere, and the stability of the device itself is greatly improved. Huge potential area in organic and high-quality display technology
6 6
替换页（细则第 26条)
附图说明 Replacement page (Article 26) BRIEF DESCRIPTION OF THE DRAWINGS
图 1是现 ¾ 机共轭聚合物发光二极管的结构示意图； Figure 1 is a schematic diagram of the structure of an existing organic conjugated polymer light emitting diode;
图 2为以铝作为阴极的器件的能带图； FIG. 2 is an energy band diagram of a device using aluminum as a cathode; FIG.
图 3是本发明有 iy高^^发光二极管结构示意图； FIG. 3 is a schematic structural diagram of a light emitting diode with an iy height of the present invention;
图 4是比较聚 [2—甲氧基 (5- (2，一乙基） -B¾«-l, 4—苯乙炔） ] (MEH-PPV)材料、用 铝作阴极时有无 P1层的器件的发光亮度及发光外量子效率曲线图； Figure 4 compares the presence or absence of a P1 layer when poly [2-methoxy (5- (2, monoethyl) -B¾ «-l, 4-phenylacetylene)] (MEH-PPV) material is used as a cathode Curve of luminous brightness and external quantum efficiency of the device;
图 5是比较发绿光的苯 S¾代聚对苯乙炔（P- PPV)、用金作阴极时有无 PI层的器件的发光亮度 及发光外量子效率曲线图； Fig. 5 is a graph comparing the luminous brightness and the external quantum efficiency curve of a device emitting green light benzene S¾-generation poly-p-phenylacetylene (P-PPV) and a device with or without a PI layer when gold is used as a cathode;
图 6是比较发蓝光的聚笏 pro用金作阴极时有无 PI层的器件的发光亮度及发光外量子效率曲线 图； FIG. 6 is a graph comparing the luminous brightness and the luminous external quantum efficiency of a device with or without a PI layer when using gold as a cathode for a blue-emitting Poly Wat Pro;
图 7是图 7中比较发红光的 ffl- PPV用铝作阴极时， 有无 P1层的器件的发光亮度及发光外量子 效率曲线图。 Fig. 7 is a graph showing the luminous brightness and the external light emitting quantum efficiency of the device with or without the P1 layer when the red-emitting ffl-PPV uses aluminum as a cathode in Fig. 7;
具体实 式 Concrete form
以下实例将对本发明所提出的 B组分单体进行说明， 但本发明将不限于所列之例。 实施例 1: 2， 7-二溴笏的制备 The following examples will illustrate the B-component monomer proposed in the present invention, but the present invention will not be limited to the listed examples. Example 1: Preparation of 2,7-dibromo
按 1997年世界专利 W0 99 05184公开的方法和 "化学材料" (Chem. Mater) 11 (1997) 11083公开 的¾¾制备 2， 7 -二溴芴。称取芴（16.6克， 0. 1摩尔)， 铁粉（88毫克， 1.57毫摩尔）倒 ΛΗ口瓶 中， 加 ΛΗ氯甲烷 10045†， 冰水浴冷却， 从直压漏斗滴加溴 (35.2 克， 0.22摩尔）和 35 «三氯甲烷的混合溶液， 滴加时瓶内 ¾^¾M; 5°C0 反应完毕， 过滤， 用氯 仿重结晶， 得白色晶体（26.9克， 83%)。 N R和 GOMASS测试表明为目标产物 2， 7-二溴笏。
实施例 2: 2， 7-二溴" 9， 9~二取代笏的制备 替换页（细则第 26条)
以制备 2， 7_二溴"， ^二正雜笏为例予以说明。按 1997年世界专利 TO 99 05184公开的方法 和 "化学材料" (Chem Mater) 11 (1997) 11083公开的旅制备 2， 7 -二溴 ~9， 9~二正辛基荷。取实 施例 1所得 2， 7-二溴笏（9.72克， 0.03摩尔)， 苄基三乙基氯化铵（0.07克， 0.3纏尔）倒 ΛΗ 口瓶中， 加入 90新二甲基亚砜， 45毫升重量比 5( /。的氢氧化钠水溶液， 室温下剧烈搅拌形成悬浮 液， 滴加卜溴正辛垸（12. 5克， 65毫摩尔)， 继续搅拌 3小时， 然后用***萃取， 合并***相， 用 饱和氯化钠水溶液洗漆， ¾K硫酸 燥。蒸去 ^ ，用正己烷作洗脱剂 ¾¾析徵屯，得白色结晶。2,7-Dibromofluorene was prepared according to the method disclosed in the 1997 world patent WO 99 05184 and disclosed in "Chem. Mater" 11 (1997) 11083. Weigh tritium (16.6 g, 0.1 mol), pour iron powder (88 mg, 1.57 mmol) into a ΛΗ mouth bottle, add ΛΗchloromethane 10045 †, cool in an ice water bath, and add bromine (35.2 g) dropwise from a direct pressure funnel. , 0.22 mol) and a mixed solution of 35 «trichloromethane while dropping bottle ¾ ^ ¾M; 5 ° C 0 the mixture was then filtered and recrystallized from chloroform to give white crystals (26.9 g, 83%). NR and GOMASS tests indicated the target product 2,7-dibromo. Example 2: Preparation of 2,7-dibromo "9, 9 ~ di-substituted hydride replacement sheet (Article 26 of the detailed rules) Take the preparation of 2,7-dibromo ", ^ dizhenzahuhu as an example. According to the method disclosed in the 1997 world patent TO 99 05184 and the" Chem Mater "11 (1997) 11083, the process 2 , 7-dibromo ~ 9, 9 ~ di-n-octyl hydrazone. Take 2,7-dibromo (9.72 g, 0.03 mole) obtained in Example 1, benzyltriethylammonium chloride (0.07 g, 0.3 Er) pour ΛΗ mouth bottle, add 90 neo dimethyl sulfoxide, 45 ml of sodium hydroxide aqueous solution with a weight ratio of 5 (/%), stir vigorously at room temperature to form a suspension, and dropwise add bromo-n-oxine (12.5 G, 65 mmol), continued stirring for 3 hours, then extracted with ether, combined the ether phases, washed with a saturated sodium chloride aqueous solution, dried with ¾K sulfuric acid. Evaporated ^, and n-hexane as the eluent ¾ ¾ Obtained white crystals.
NMR和 GOMASS测试表明为目标产物 2， 7-二溴 ， 9~二正辛基荷。 NMR and GOMASS tests showed that the target product was 2, 7-dibromo, 9-di-n-octyl charge.
2， 7 -二溴一9， 9 "二取代笏中取代基包括： 正己基， 正辛基， 2—乙基 Β¾， 癸基等， 但不仅限于 此。
实施例 3: 3, 6" "二溴咔唑的制备 The 2,7-dibromo-9,9 "di-substituted substituents include, but are not limited to, n-hexyl, n-octyl, 2-ethyl beta, decyl, and the like. Example 3: Preparation of 3, 6 "" dibromocarbazole
在 1000毫升三口錄中加入咔唑（12.54克， 75毫摩尔)， 375毫升精制二硫化碳和 24毫升 ¾ 吡啶,用机械搅拌器边搅拌边用冰水冷却，当冷却至 0Ό，开始滴加溶于 75毫升二硫化碳的液溴 (28· 30 克， 177雜尔)，约滴加 1小时。滴完后撤去 嘰置，逐渐升至 15°C，保持15°〇下搅拌2.5小时, 反应结束。将反应液倒入 400毫升稀盐酸中，有淡黄色沉淀生成，过滤，用稀的氢氧化钠溶液洗漆 3 次， 再用蒸馏水洗涤至中性， 干燥。用¾*乙醇重结晶， 烘干， 得白色针状晶体， 产率 83%。 1羅 和 GC"MASS测试表明为目标产物 3， 6~二溴咔唑。
实施例 4: 3， 6~二溴 取代咔唑的制备 Add carbazole (12.54 g, 75 mmol), 375 ml of refined carbon disulfide, and 24 ml of ¾ pyridine to 1000 ml of the three-portion record. Cool with ice water while stirring with a mechanical stirrer. When cooled to 0 ° C, start to dissolve dropwise. 75 ml of carbon bromide liquid bromine (28.30 g, 177 heur) was added dropwise for about 1 hour. After dripping, the mixture was removed, gradually raised to 15 ° C, and kept at 15 ° C and stirred for 2.5 hours, and the reaction was completed. The reaction solution was poured into 400 ml of dilute hydrochloric acid, and a pale yellow precipitate formed, filtered, washed with dilute sodium hydroxide solution three times, and then washed with distilled water to neutrality and dried. It was recrystallized with ¾ * ethanol and dried to obtain white needle crystals with a yield of 83%. 1 Luo and GC "MASS test showed the target product 3, 6 ~ dibromocarbazole. Example 4: Preparation of 3, 6 ~ dibromo-substituted carbazole
以制备 3, 二溴 2-乙基 BS咔唑为例予以说明。在氮气 ί¾ί户下， 于 250毫升 中加入 60 替换页（细则第 26条)
%的氢化钠（1. 104克， 27.6毫摩尔）和 25斬四氢呋喃，纖拌边滴加溶于 25新四氢呋喃的 3, 6 "二溴咔唑（5克， 15.4毫摩尔）溶液，此时有小气泡生成，溶液也由灰白色变淡乡絶， 常温搅拌一 段时间后， 将反应 升至溶液回流， 加入 4.5毫升 溴- 2-乙基己烷（486克， 25.2¾0尔)， 在 回流下反应 24小时， 结束反应。蒸去髓 U， 加 ΛΖ:氯甲烷和水进行萃取， 用水洗漆有娠 4次， 加 入无水硫酸^ F燥， 除去溶剂， 得淡黄色粘稠状液体， 用乙酸乙脂和正己焼混合溶剂（1:10)作洗脱 剂柱层霞一步職 U，得到白色晶体，产率 75%。¾NMR和 GCH1ASS测 i錄明为目标产物 3, 6"二溴 -2- 乙基己基咔唑。 Take the preparation of 3, dibromo 2-ethyl BS carbazole as an example. Under nitrogen, add 60 replacement pages to 250 ml (Article 26) % Sodium hydride (1.104 g, 27.6 mmol) and 25 chopped tetrahydrofuran, and a solution of 3, 6 "dibromocarbazole (5 g, 15.4 mmol) dissolved in 25 new tetrahydrofuran was added dropwise while stirring, at this time Small bubbles were formed, and the solution also turned pale from off-white. After stirring at room temperature for a period of time, the reaction was brought to reflux and 4.5 ml of bromo-2-ethylhexane (486 g, 25.2¾0 g) was added. Under reflux The reaction was completed for 24 hours. The reaction was completed. The bone marrow was distilled off, and ΛZ: chloromethane and water were added for extraction. The lacquer was washed 4 times with water, dried with anhydrous sulfuric acid ^ F, and the solvent was removed to obtain a pale yellow viscous liquid. A mixed solvent of ethyl acetate and n-hexane (1:10) was used as the eluent. The white layer was obtained with a yield of 75%. ¾ NMR and GCH1ASS showed that the target product was 3, 6 "dibromo- 2-ethylhexylcarbazole.
3, 二溴 -N-取代昨唑中取代 ^括： 正己基， 正辛基， 2—乙基己基等， 但不仅限于此。
实施例 5: 9， 9~二取代 -2， 7 -二硼酸酯芴的制备 3, Dibromo-N-substituted yttriazoles include: n-hexyl, n-octyl, 2-ethylhexyl, etc., but is not limited thereto. Example 5: Preparation of 9, 9 ~ disubstituted-2,7-diborate hydrazone
以制备 9， 9"二正辛基- 2， 7-二硼酸酯芴为例予以说明。按"大分子" (ferofflolecules) 30 (1997) 7686公开的 制备 9， ^二正 H 7—二硼酸酷莉。取实施例 2所得干燥的 2， 7 -二溴 "9， 9~二 正辛基莉（5.6克， 10· 22毫摩尔）溶于職 I仟燥后的 130毫升四氢呋喃 (W)中， 千觸气傲户下 ~78°C时滴加 20 ¾^正丁基锂（1.6摩尔 /升，正己烷为溶剂， 32¾ 尔)，滴毕，反应混合物在 -78 °C下搅拌至少 1. 5小时， 随后快速加入 2_异丙氧 ¾"4， 4, 5， 5 -四甲 ¾~1， 3, 2-乙二氧基硼酸酯 (25 毫升， 123.24毫摩尔)， 在- 78Ό下继续搅拌 2小时。然后让反应混合物逐渐升至室温， 搅拌反应至 少 36小时。随后反应混合物倒入水中，用***萃取，合并***相，用盐水洗涤并用无水硫酸^ T燥， 蒸去翻， 残余物用四氢呋喃和甲醇重结晶， 进一步用観析提纯（赚， 正己烷： 乙酸乙酉 ^9: 1 为灘剂)， 得白色固体。 匿， GC«S ^¾素分析表明所得为目标产物 9， 9"二正辛 ¾"2， 7二 硼酸酯 Take the preparation of 9, 9 "di-n-octyl-2, 7-diborate gadolinium as an example. According to the preparation of" Ferofflolecules "30 (1997) 7686, the preparation of 9, 9-di-n-H 7-2 Coolie borate. Take the dried 2,7-dibromo "9, 9 ~ di-n-octyl (5.6 g, 10.22 mmol) obtained in Example 2 and dissolve it in 130 ml of tetrahydrofuran (W ), At a temperature of ~ 78 ° C, add 20 ¾ ^ n-butyllithium (1.6 mol / L, n-hexane as the solvent, 32¾ er) dropwise, and the reaction mixture is stirred at -78 ° C. At least 1.5 hours, followed by the rapid addition of 2-isopropoxy ¾ "4, 4, 5, 5 -tetramethyl ¾ ~ 1, 3, 2-ethanedioxyborate (25 ml, 123.24 mmol), Stirring was continued at -78 ° C for 2 hours. Then the reaction mixture was gradually warmed to room temperature, and the reaction was stirred for at least 36 hours. The reaction mixture was then poured into water, extracted with ether, the ether phases were combined, washed with brine and dried over anhydrous sulfuric acid Distilled off, the residue was recrystallized with tetrahydrofuran and methanol, and further purified by decantation (earn, n-hexane: ethyl acetate ^ 9: 1 as a beach agent), to obtain Solid. Hide, GC «S ^ ¾ vegetable analysis revealed that the obtained target product 9, 9 'di-n-octyl ¾" 2, 7 diboronate
9， 9~二取代 -2， 7-二硼酸酯芴中取代基包括： 正己基， 正辖， 2-乙基己基， 癸基， 但不仅限 于此。 The substituents in 9, 9 ~ disubstituted -2, 7-diborate hydrazone include: n-hexyl, n-hexyl, 2-ethylhexyl, decyl, but not limited thereto.
9 9
替换页（细则第 26条)
实施例 6: ^取代 -3， 6"二硼酸酯咔唑的制备 Replacement page (Article 26) Example 6: Preparation of ^ -substituted-3, 6 "diborate carbazole
以制备 3， ^-- (4, 4, 5， 5—四甲 H 3， 2—二氧硼酸酯) (2' —乙基己基）咔唑为例予以说 明。在三口 中加入 3, 二溴 -N- 2_乙基己基咔唑（4. 5克， 10. 30¾ 尔）和 80毫升四氢呋喃， 搅拌均匀后， 将反应液 口至- 78Ό， 滴加 24新 2Μ正丁基锂（48毫摩尔)。滴加完毕后， 继難 - 78°C搅拌 2小时， 然后一次性加入 2-异丙氧 S~4, 4， 5， 5-四甲 ¾"1， 3, 2-乙二氧基硼酸酯 (25 毫升， 123. 24* 尔)， 继餘- 78°C搅拌 2小时， 然后将反应 升至室温， 反应 36小时， 结束反 应。用乙酵取， 饱和食盐水洗涤 4次， ^mm , 除去灘 u， 用乙酸乙脂和 正己綜混合^ HJ (1： 9)为洗脱剂柱层析提纯， 得白色晶体， 产率 45%。 ¾NMR和 GC4 SS测试表明 为目标产物 3， 6 -二 (4， 4, 5, 5 -四甲 H， 3， 2-二氧硼酸酯) (2' -乙基己基）咔唑。 Take the preparation of 3, ^-(4,4,5,5-tetramethylH 3,2-dioxoborate) (2'-ethylhexyl) carbazole as an example. Add 3, dibromo-N- 2 -ethylhexylcarbazole (4.5 g, 10.30¾ mol) and 80 ml of tetrahydrofuran to the three ports, and after stirring well, bring the reaction solution to -78Ό and add 24 drops of new 2M n-butyllithium (48 mmol). After the addition is complete, stir at -78 ° C for 2 hours, and then add 2-isopropoxy S ~ 4, 4, 5, 5-tetramethyl ¾ "1, 3, 2-ethanedioxyboronic acid in one portion. Ester (25 ml, 123.24 * ul), and then stirred at -78 ° C for 2 hours, then the reaction was warmed to room temperature, and the reaction was completed for 36 hours. The reaction was terminated with ethyl acetate, washed with saturated brine 4 times, ^ mm , Remove the beach, and use ethyl acetate and n-hexyl ^ HJ (1: 9) as eluent column chromatography to obtain white crystals, yield 45%. ¾ NMR and GC4 SS test showed the target product 3, 6 -Bis (4,4,5,5-tetramethylH, 3,2-dioxoborate) (2'-ethylhexyl) carbazole.
^取代- 3, 二硼酸酯咔唑中取代¾ ^括： 正己基， 正辛基， 2-乙基己基等， 但不仅限于此。
^ Substitution-3, Substitution in carbazole ¾ ^ include: but not limited to n-hexyl, n-octyl, 2-ethylhexyl and the like.
以下实例将对本发明所提出的 A组分单体进行说明， 但本发明将不限于所列之例。 实施例 7: 9位带有含胺基功能团侧链的二溴笏的制备 The following examples will illustrate the A component monomers proposed in the present invention, but the present invention will not be limited to the listed examples. Example 7: Preparation of dibromo group at side 9 with amine-containing functional group side chain
以制备 ¾ 7-二溴 - 9, 9-双（N 二甲基胺丙基）芴为例予以说明。在 25QiL三口瓶中分别加入 ：)、 4g (12 m mol) 2, 7 -二溴芴、 80 mg四丁基溴化铵， 搅拌均匀后滴加入 ½L 5(1 NaCH 7溶 m. 反应 30 min,然后滴加入 lOmL已经用 NaOH中和过的含有 6g (38 m mol) N, ^二甲基氯丙胺 盐酸盐的水溶液。反应 6 h后， 向反应体系中加入 5M水， 溶解掉反应中生成的盐后， 用 300 ui乙 醚分三次萃取反应液， 有机相用饱和食盐水洗漆三次后， 用¾7硫隱干燥， ffi蒸出髓 !1， 粗产 Take the preparation of ¾ 7-dibromo-9, 9-bis (N dimethylaminopropyl) 芴 as an example. In a 25QiL three-necked flask, add :), 4g (12 m mol) 2, 7-dibromofluorene, 80 mg of tetrabutylammonium bromide, and add ½L 5 (1 NaCH 7 in m. Then, 10 mL of an aqueous solution containing 6 g (38 m mol) of N, dimethyl chloropropylamine hydrochloride neutralized with NaOH was added dropwise. After 6 hours of reaction, 5 M water was added to the reaction system to dissolve the reaction. After the generated salt, the reaction solution was extracted three times with 300 ui ether, and the organic phase was washed with saturated brine three times, and then dried with ¾7 sulfur, and the pulp was distilled off.
10 10
替换页（细则第 26条)
物在甲醇和水的混合赚 !J中重结晶后得到白色针状固体， 产率 51%。 1膽和 13隱测 i錄明为目标 产物 ¾ 7—二溴- 9, 9-¾ (Ν，Ι^·二甲基胺丙基）芴。 Replacement page (Article 26) The mixture was mixed with methanol and water to obtain a white needle-like solid after recrystallization in J, yield 51%. 1 gall and 13 glyphs were recorded as the target product ¾ 7-dibromo-9, 9-¾ (N, 1 ^ · dimethylaminopropyl) 芴.
2， 7—二溴^， 9 "二 Β¾«代荷中取代基包括： Ν，^二甲基胺丙基， Ν，Ν—二甲基胺乙基， Ν， "二甲 基胺己基， ΝΈ乙基胺乙基等， 但不限于此。 Substituents in 2,7-dibromo ^, 9 "di-B¾" substitutions include: Ν, ^ dimethylaminopropyl, Ν, Ν-dimethylaminoethyl, Ν, "dimethylaminohexyl, NΈethylaminoethyl and the like are not limited thereto.
以制备 ¾ 7 -二溴→, 9~双（磺酸钠丁基）芴为例予以说明。在 500ml三口瓶中， 把 15g二溴笏溶 于 45mlDMS0中。再加入 1.2g四丁基溴化胺和 15ml50%的 Naffl水溶液。溶液很 为橙红色， 呈« 态， 加热后反应 1小时。把 18g 1，4- Butanesultone和 15mlDMS0用恒压漏斗滴入三口瓶中， 大约一小 商完。 反应一天后， 停止搅拌， 反应结束。在三口瓶中加入少量丙酮后， 抽滤。抽滤后得到的固 條丙酮和水的混合赚中重结晶后得到白色固体，最后榭寻到的产物真空干燥，产率： 73%。 1匿 和13 CNMR测试表明为目标产物 ¾ 7-二溴 , 9 "双（磺 丁基）芴。 Take the preparation of ¾ 7 -dibromo →, 9 ~ bis (sodium sulfonate butyl) 芴 as an example. In a 500 ml three-necked bottle, 15 g of dibromo was dissolved in 45 ml of DMS0. An additional 1.2 g of tetrabutylamine bromide and 15 ml of a 50% aqueous solution of Naffl were added. The solution was orange-red in «state and reacted for 1 hour after heating. 18g of 1,4- Butanesultone and 15ml of DMS0 were dropped into a three-necked bottle with a constant pressure funnel. After one day of reaction, the stirring was stopped and the reaction was completed. After adding a small amount of acetone to the three-necked flask, suction filtration was performed. A mixture of solid acetone and water obtained after suction filtration was recrystallized to obtain a white solid. The final product was dried under vacuum. Yield: 73%. 1 and 13 C NMR tests indicated the target product was ¾ 7-dibromo, 9 "bis (sulfobutyl) fluorene.
2， 7—二溴^ 9， 9~二磺酸 代芴中取代基包括： 磺 丙基， 磺酸钾丙基， 磺 丁基， 磺酸 钾丁基等， 但不限于此。 The substituents in 2,7-dibromo ^ 9, 9 ~ disulfonium include: sulfopropyl, potassium sulfopropyl, sulfobutyl, potassium sulfonate and the like, but are not limited thereto.
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替换页（细则第 26条)
实施例 9: 9位带有含羧酸基功能团侧链的二溴誦制备 Replacement page (Article 26) Example 9: Preparation of dibromo group 9 with a carboxylic acid group-containing functional side chain
以制备 ¾ 7-二溴" ¾ ^双（羧酸钠戊基）芴为例予以说明。在 500ml三口瓶中， 把 15g二溴荷溶 于 45mlHS0中。再加入 1.2g四丁基溴化胺和 15ml5(^的 Naffl水溶液。溶液很†»为橙红色， 呈« 态， 加热后反应 1小时。慢慢加 Λϋ»的 6 "溴代己酸， 反应在常温下搅拌一天后， 停 拌， 加入 大量丙酮， 滤出生成的沉淀， 将粗品在 丙酮的混合^ 中重结晶后即得目标产物。 Take the preparation of ¾ 7-dibromo "¾ ^ bis (sodium pentyl carboxylate) hydrazone as an example. In a 500 ml three-necked bottle, 15 g of dibromobenzene is dissolved in 45 ml of HSO. 1.2 g of tetrabutylamine bromide is added And 15ml of Naffl aqueous solution. The solution is † »orange-red, in the« state, and reacted for 1 hour after heating. Slowly add Λϋ »6" bromohexanoic acid. After stirring at room temperature for one day, stop mixing. A large amount of acetone was added, the resulting precipitate was filtered off, and the crude product was recrystallized from a mixture of acetone to obtain the target product.
以制备 3， 6-二溴 4-磺睡基丁基咔唑为例予以说明。在氮气 ί 户下，于 250毫升烧瓶中加入 60%的氢化钠（1. 104克， 27.6毫摩尔）和 25 四氢呋喃， 拌边滴加溶于 25毫升四氢呋喃的 ¾ 6-二溴咔唑（5克， 15.4轉尔）溶液， 此时有小气泡生成， 溶液也由灰白色变淡馳， 常温搅 拌一段时间后， 将反应 升至溶液回流， 加入过量的 1, 4- Butenesultone, 在回流下反应 24小时， 结束反应。将反应液过滤后得到的沉淀在水中重结晶后即得目标产物。 Take the preparation of 3, 6-dibromo 4-sulfobutylcarbazole as an example. Under a nitrogen atmosphere, 60% sodium hydride (1.104 g, 27.6 mmol) and 25 tetrahydrofuran were added to a 250 ml flask, and ¾ 6-dibromocarbazole (5 G, 15.4 rpm) solution, small bubbles were formed at this time, and the solution also turned from off-white to light white. After stirring at room temperature for a period of time, the reaction was brought to reflux, and an excess of 1, 4- Butenesultone was added. The reaction was carried out under reflux for 24 hours. Hours, end the reaction. The precipitate obtained after filtering the reaction solution was recrystallized from water to obtain the target product.
含磺酸基功能团侧链的二溴咔唑的侧联取代基包括： 磺 丙基， 磺酸钾丙基， 磺酸钠丁基， 磺酸钾丁基等， 但不限于此。 The pendant substituents of the dibromocarbazole containing a sulfonic acid functional group side chain include: sulfopropyl, potassium sulfopropyl, sodium sulfonate butyl, potassium sulfonate, but are not limited thereto.
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替换页（细则第 26条)
Replacement page (Article 26)
按 "有机化学会志" (J. Org. Chem ) 57， (1992 ) 6749-6755公开的方法制备 4， 7 -二溴—2， 1， 3-苯麵二唑。溴化 2， 1， 3—苯并噻二挫得 4， .7—二溴 -2, 1， 3-苯并噻二唑， 产率 95%。称取 4， 7- 二溴- 2， 1， 3 -苯并噻二唑（5.88克， 0. 02摩尔)， 加入乙醇 190毫升， 形成悬浮液， 0°〇日中滴加硼氢 化钠（14克， 0. 37摩尔)，室温下混合物搅拌反应 20小时，蒸去翻，得 3， 6~二溴- 1， 2-苯二胺（4 5 克)， 淡黄色固体， 产率 85%。取 3， 6 -二溴 - 1， 2-苯二胺（2. 7克， 10聽尔)， 乙醇 55毫升， 回流， 滴加二氧化硒（1. 17克， 10. 5麵尔） 7K溶液（热水 22毫升)， 反应混合物回流 2小时， 过滤， 得 黄色沉淀 3克， 产率 8 。 经1 HNMR， GCHMASS, 元素分析表明为目标产物 4， 7-二溴- 2， 1， 3-苯擁 二唑。
聚合物的制备 4, 7-Dibromo-2,1,3-benzimidazole was prepared according to the method disclosed in J. Org. Chem 57, (1992) 6749-6755. Bromide 2,1,3-benzothiadibromide gave 4, .7-dibromo-2,1,3-benzothiadiazole with a yield of 95%. Weigh 4,7-dibromo-2,1,3-benzothiadiazole (5.88 g, 0.02 mole), add 190 ml of ethanol to form a suspension, and drop sodium borohydride ( 14 g, 0.37 mol), the mixture was stirred and reacted at room temperature for 20 hours, and evaporated to obtain 3,6-dibromo-1,2-phenylenediamine (45 g), a pale yellow solid, yield 85% . Take 3, 6-dibromo-1,2-phenylenediamine (2.7 g, 10 torr), 55 ml of ethanol, reflux, and dropwise add selenium dioxide (1.17 g, 10.5 tol) 7K The solution (22 ml of hot water), the reaction mixture was refluxed for 2 hours, and filtered to obtain 3 g of a yellow precipitate with a yield of 8%. 1 HNMR, GCHMASS, and elemental analysis showed that it was the target product of 4, 7-dibromo-2, 1, 3-benzophenadiazole. Preparation of polymers
(1)侧链带有 ¾¾功能团的聚合物的制备 (1) Preparation of polymer with ¾¾ functional group in side chain
取 9， 9"二取代 -2， 7-苟二硼酸酯 5毫摩尔， 带有胺基的二溴化合物 5毫摩尔， 溶于 30毫升甲苯中， 在氮气 1¾户下加入 5滴相转移催化剂 AUQUAT 336, 舰 70"80毫克， 2M碳隱水溶液 10毫升。 混合物加热至回流， 搅拌反应 8小时， 然后加入 1毫升溴苯封端， 继续反应 3小时。反应混合物冷 却， 在搅拌下慢慢倾入 1升甲醇溶液中， 过滤， 淀出的聚合物。用 300毫升甲磨先涤， 干燥, 然后溶于少量四氢呋喃中， 在搅拌下慢慢倾入 1升甲藤液中， 过滤出沉淀， 倒入 500毫升丙酮中， 搅拌 5小时， 过滤， 真空下干燥， ί#¾聚物。 Take 5 mmol of 9, 9 "disubstituted-2, 7-go diborate, 5 mmol of dibromo compound with amine group, dissolve in 30 ml of toluene, add 5 drops of phase transfer under nitrogen 1¾ Catalyst AUQUAT 336, ship 70 "80 mg, 2 ml of 2M carbon solution in water. The mixture was heated to reflux, the reaction was stirred for 8 hours, then 1 ml of bromobenzene was added to end the reaction, and the reaction was continued for 3 hours. The reaction mixture was cooled, slowly poured into 1 liter of a methanol solution with stirring, and the polymer precipitated was filtered. Wash with 300 ml nail polish, dry, then dissolve in a small amount of tetrahydrofuran, slowly pour into 1 liter of methyl vinegar solution with stirring, filter out the precipitate, pour into 500 ml of acetone, stir for 5 hours, filter, and dry under vacuum Ί # ¾ 聚。.
(2)侧链带有 安盐基功能团的聚合物的制备 (2) Preparation of a polymer with a functional group on the side chain
取带有胺基的聚合物 100¾， 加入 4Μ的 THF及 IQIIL的 DMS0后再加入过量的溴乙垸或碘甲烷， 反 Take the polymer with amine group 100¾, add 4M THF and IQIIL DMS0, and then add excess bromoacetamidine or methyl iodide.
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替换页（细则第 26条）
应体系在 50Ό下反应 5天， ¾5蒸馏除去大部分的 W及未反应完全的溴乙烷或碘甲烷，加入 80mL的 '乙酸乙酯或丙酮沉淀产物， 离心分离并用氯仿、 四氢 B夫喃洗涤后在 50°C下真空干燥得到产物。 Replacement page (Article 26) The reaction system was reacted at 50 ° C for 5 days. ¾5 was distilled to remove most of the W and unreacted bromoethane or methyl iodide. 80mL of 'ethyl acetate or acetone was added to precipitate the product. The product was centrifuged and chloroform and tetrahydrobran After washing, the product was obtained by drying under vacuum at 50 ° C.
(3)侧链带^^ 能团的聚合物的制备 (3) Preparation of polymer with side energy band
带有磺酸基的二溴化合物单体 5毫摩尔、 1H硼酸 5纏尔、25呢醋舰，溶于 50mlDMF 8( PH=10 的缓冲溶液， 反应在 ^气 户下， 回流 3天。然后冷却到室温， 将反应液在丙酮中沉淀， 粗品溶于 水后， 用截止分子量为 3500的膜透析三天。然后再在丙酮中沉淀真空干燥后得到灰白色固体产物。 下面以聚 [9， ^二辛基笏 ~9， 9"双（N，N"二甲基胺丙基）芴] (pi) , 侧链带有磺酸盐基功能团的 聚合物， PF-S0^ia(P2) , 以及含有窄带隙的三组分共聚物 (窄带隙的单体苯并噻二唑) (P3)^ 说明， 对比一般的透明阳极 /发光共轭聚合物 /阴极即所谓单层结构， 采取多层结构一在发光共轭聚合物和 功函数较高的、环境稳定性、适应性好的金属如铝、金之间***一薄层的聚合高^?电解质薄膜时， 将大大降低少数纖子电子的注入势垒， 从而增强电子的注入效率， 平衡双极载流子， 使得空穴一 电子复合， 进而辐射发光的效率（电致发光的内量子效率）得以改善。 实施例 13 Dibromo compound monomer with sulfonic acid group 5 mmol, 1H boric acid quinone, 25% vinegar, dissolved in 50ml of DMF 8 (PH = 10 buffer solution, the reaction was carried out under air, and refluxed for 3 days. Then After cooling to room temperature, the reaction solution was precipitated in acetone. After the crude product was dissolved in water, it was dialyzed against a membrane with a molecular weight of 3500 for three days. Then it was precipitated in acetone and dried under vacuum to obtain an off-white solid product. Dicaprylic ~ 9, 9 "bis (N, N" dimethylaminopropyl) 芴] (pi), polymer with sulfonate functional group in side chain, PF-S0 ^ ia (P2) , And a three-component copolymer containing a narrow band gap (narrow band gap monomer benzothiadiazole) (P3) ^ Compared with the general transparent anode / light-emitting conjugated polymer / cathode, the so-called single-layer structure, it takes more Layer structure: When a thin polymer electrolyte is inserted between a light-emitting conjugated polymer and a high work function, environmentally stable, and adaptable metal such as aluminum and gold, a small number of fibers will be greatly reduced. The electron injection barrier, thereby enhancing the electron injection efficiency and balancing the bipolar carriers, so that A hole-electron recombination, and thus a luminescent efficiency (internal quantum efficiency of the organic electric luminescence) is improved. Example 13
ITO导电玻璃， 方块电阻〜 20 Ω/口， 预切割成 15毫米 X 15毫米方片。依次用丙酮、微米级 半导体专用洗涤剂、 去离子水、 异丙醇超声清洗， 氮气吹扫后置于恒温烘箱备用。 使用前， IT0 净片在氧等离子体刻蚀仪中以等离子体轰击 10分钟。 选用 PVK、 PED0T:PSSPVK购自 Aldrich公 司， 以四氯乙烷配制溶液。 PED0T:PSS水分散液（约 1% )购自 Bayer公司 缓冲层以匀胶机 (KW -4A)髙速旋涂， 厚度由溶液浓度与转速决定， 用表面轮廓仪（Tritek公司 Alpha- Tencor500 型）实测监控。 成膜后， 于恒温真空烘箱中驱除溶剂残余、 坚膜。 ITO conductive glass, square resistance ~ 20 Ω / port, pre-cut into 15 mm X 15 mm square pieces. Use acetone, micron-level semiconductor detergent, deionized water, isopropyl alcohol, ultrasonic cleaning in order, and then put them in a constant temperature oven after purging with nitrogen. Before use, IT0 nets were bombarded with plasma in an oxygen plasma etcher for 10 minutes. PVK, PED0T: PSSPVK were purchased from Aldrich, and the solution was prepared with tetrachloroethane. PED0T: PSS water dispersion (about 1%) was purchased from Bayer's buffer layer and spin-coated with a homogenizer (KW-4A). The thickness was determined by the solution concentration and speed. A surface profiler (Tritek Alpha-Tencor500) was used. ) Measured monitoring. After film formation, the solvent residue and hard film were driven out in a constant temperature vacuum oven.
荧光共轭聚合物于干净瓶中称量后， 转入氮气保护成膜专用手套箱 (VAC公司）， 在甲苯中 溶解，以 0.45微米滤膜过滤。聚合物发光层最佳厚度为 70〜90纳米。膜厚用 TENCORALFA-STEP- 500 表面轮廓仪测定。 将 P1在甲醇（加入少量乙酸）中溶解， 配制成 0.04% 0. 两种浓度的溶液。利 After the fluorescent conjugated polymer was weighed in a clean bottle, it was transferred to a nitrogen-resistant film-forming glove box (VAC company), dissolved in toluene, and filtered through a 0.45 micron filter membrane. The optimal thickness of the polymer light-emitting layer is 70 to 90 nm. The film thickness was measured with a TENCORALFA-STEP-500 surface profiler. P1 was dissolved in methanol (a small amount of acetic acid was added) to prepare a 0.04% 0. two concentration solution. Profit
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用勾胶机在发光高分子层上旋转涂敷生成一薄层 P1聚合物，其厚度当用 0.04% 0. 度时分别为 1和 5纳米。铝或金电极蒸镀在真空镀膜机中真空度达到 3X 10¾以下时完成。 «速率与各层电 极之厚度由石英振子膜厚监测仪（SBHOO型, Sycon公司）实时监控。器件的发光区域由掩模与 IT0 ¾S覆盖的区域确定为 0. 15平方厘米。所有制备过程均在提供氮气惰性氛围的手套箱内进行器件的 电流一电压特性，发光的强度和外量子效率由 Keithley236电流电压源一测量系舰一个经校正的硅 光二极管测得。 Replacement page (Article 26) Spin coating on the light-emitting polymer layer with a glue hook machine produces a thin layer of P1 polymer, the thickness of which is 1 and 5 nanometers when 0.04% 0. degree is used. Aluminum or gold electrode evaporation is completed when the vacuum degree in the vacuum coating machine reaches 3X 10¾ or less. «The speed and the thickness of each layer of electrode are monitored in real time by a quartz oscillator film thickness monitor (SBHOO type, Sycon company). The light emitting area of the device was determined to be 0.15 cm 2 by the area covered by the mask and IT0 ¾S. All the preparation processes were performed in a glove box providing a nitrogen inert atmosphere. The current-voltage characteristics, luminous intensity and external quantum efficiency were measured by a Keithley236 current-voltage source-measurement system and a calibrated silicon photodiode.
采用 90纳米厚的聚 [2-甲氧基（5— (2， 一乙基）一己纖一 1， 4一苯乙炔） ] (MEtt-PPV)共 轭聚合物薄膜为发光层， 分别高功函数的 A1 (44电子伏特)， Au (5.3电子伏特)， 以不同浓度的交替 (2， 5—双（3— [N，F "二乙基胺基] 1—氧丙 ¾~1， 4—苯—共^， 9 "二 ^¾笏共聚物 (P1) 的甲醇溶液下旋涂 P1的薄层在发光层; ±作为电子注入层,在电子注入层 P1之上真空蒸镀覆盖以铝或金的双层结构作 为阴极， 制作发出橘红颜色光的聚合物发光二极管。 为显示本发明所采用的电子注入层的效果， 采 用低功函数的 Ba(2.7电子伏特) /A1和高功函数的 Al (4.2电子伏特）及 Au(5. 3电子伏特）直接蒸镀在 ¾ MEHPPV之上所制备的常规发光器件作为参比器件，测量结果列于表 1。图 4中比较聚 [2—甲氧 基（5— (2， 一乙基）一己基氧一 1， 4—苯乙块） ] (MEH-PPV)材料、用铝作阴极时有无 P1层的器 件的发光亮戯发光外量子效率。 A 90-nm-thick poly [2-methoxy (5- (2, monoethyl) -hexadecane-1,4-phenyleneacetylene]] (MEtt-PPV) conjugated polymer film was used as the light-emitting layer. Function of A1 (44 electron volts), Au (5.3 electron volts), alternating at different concentrations (2, 5-bis (3- [N, F "diethylamino] 1-oxypropyl ¾ ~ 1, 4 —Benzene—co- ^, a thin layer of P1 is spin-coated under a methanol solution of 9 "di-copolymer (P1) in a light-emitting layer; ± as an electron injection layer, vacuum-evaporated over the electron injection layer P1 covered with aluminum A double-layered structure of gold or gold is used as a cathode to produce a polymer light emitting diode emitting orange-red light. In order to show the effect of the electron injection layer used in the present invention, a low work function Ba (2.7 electron volts) / A1 and a high work function are used. The conventional light-emitting device prepared by directly vapor-depositing Al (4.2 electron volts) and Au (5.3 electron volts) on ¾ MEHPPV was used as a reference device, and the measurement results are shown in Table 1. The comparative poly [2— Methoxy (5- (2, monoethyl) -hexyloxy-1,4-phenylethyl block)] (MEH-PPV) material, with or without P1 layer when using aluminum as cathode The device's luminous effect shines outside quantum efficiency.
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替换页（细则第 26条)
表 1基于红光材料聚 [2—甲 (5- (2' -Z¾)一己纖一1, 4一苯乙炔） ] (MH ), 用 P1作为电子 ¾Λ层的器 件的电雜光性能， 器件结构为
mm 电子 &Λ层 阴极 电压 电流 & 夕卜 *ΐ效率 Replacement page (Article 26) Table 1 Electrical stray light performance of devices based on red light-emitting poly [2-methyl (5- (2'-Z¾) -hexadecane-1, 4-phenylphenylacetylene]] (MH), using P1 as an electron ¾Λ layer, device Structure is mm Electron & Λ Layer Cathode Voltage Current & Efficiency
(伏特） («¾) (± 方米) (Volts) («¾) (± square meters)
MEHPPV Pl(0.0 %) 铝 7.0 24.7 2247 229 MEHPPV Pl (0.0%) aluminum 7.0 24.7 2247 229
52 5.5 325 1.54 52 5.5 325 1.54
MEHPPV Pl(02%) 铝 9.0 47.4 2953 MEHPPV Pl (02%) aluminum 9.0 47.4 2953
65 52 269 136 65 52 269 136
MEHPPV Pl(0.04%) 金 6.0 46.1 34 0.019 MEHPPV Pl (0.04%) Gold 6.0 46.1 34 0.019
32 5.4 1 0.01 32 5.4 1 0.01
MEHPPV Pl(02%) 金 7.0 12.9 259 053 MEHPPV Pl (02%) Gold 7.0 12.9 259 053
6.0 52 65 033 6.0 52 65 033
参照例 Reference example
MEHPPV - 柳铝 7.0 32.1 2565 2.10 MEHPPV-Liuliu 7.0 32.1 2565 2.10
4.8 53 499 2.46 4.8 53 499 2.46
MEHPPV - 铝 7.0 43.6 214 0.07 MEHPPV-Aluminum 7.0 43.6 214 0.07
4.6 52 3.8 0.019 4.6 52 3.8 0.019
MEHPPV 金 6.0 48.0 0.04 MEHPPV Gold 6.0 48.0 0.04
由此例之结果可以充分说明对发红光的 MEHPPV常规器件， 当直接用铝或金等高功函数作阴极时 器件的量子效率比相应低功函数阴极钡的器 #ί氏得多。但当用 P1置于发光层与高功函数金属之间时， 器件的量子效率达到^^过相应低功函数金属钡作阴极的器件。 实施例 14 重复例 2将聚合物发光层置换为发绿光的 ¾¾¾***苯乙炔（ )，其它 不变。实验结 果总结于表 2。 图 5中比较发绿光的苯基取代 ¾寸苯乙炔 (P-PPV),用金作阴极时有无 P1层的器件 的发光亮戯发光外量子效率。 The results of this example can fully explain that for conventional red-lighting MEHPPV devices, when the high work function such as aluminum or gold is directly used as the cathode, the device's quantum efficiency is much higher than the corresponding low work function cathode barium device. However, when P1 is placed between the light-emitting layer and the high work function metal, the quantum efficiency of the device is higher than that of the corresponding low work function metal barium as the cathode device. Example 14 Example 2 was repeated. The polymer light-emitting layer was replaced with a green-emitting phenylacetylene (), and the others remained unchanged. The experimental results are summarized in Table 2. Figure 5 compares the green quantum efficiency of a device that emits green phenyl-substituted ¾-inch phenylacetylene (P-PPV) with and without P1 layer when gold is used as the cathode.
17 17
替换页（细则第 26条）
表 2基于就材料 P"PPV用 PI作为电子 层的器件的 ¾¾¾¾性能， 器件结构为 ITO^EDOT/ADS129 /Al (Au) m 电子 ¾Λ 阴极 mt . 外量子效率 纖 獰安） 薪方米) eo) Replacement page (Article 26) Table 2 is based on the ¾¾¾¾ performance of the device using PI as the electronic layer for the material P "PPV, and the device structure is ITO ^ EDOT / ADS129 / Al (Au) m electron ¾Λ cathode mt. External quantum efficiency fiber (Amp. Square meter) eo )
P-PPV Pl(0.04%) 铝 9.0 28.6 5804 2.56 P-PPV Pl (0.04%) Aluminum 9.0 28.6 5804 2.56
6.8 45 698 1.94 6.8 45 698 1.94
P-PPV Pl(02%) 铝 9.0 16.4 10388 7.99 P-PPV Pl (02%) Aluminum 9.0 16.4 10388 7.99
7.6 4.6 3624 10.01 7.6 4.6 3624 10.01
P-PPV 14.0 172 2 0.002 P-PPV 14.0 172 2 0.002
11.5 4.7 1 0.003 11.5 4.7 1 0.003
P-PPV Pl(0.04%) 金 11.0 272 160 0.074 P-PPV Pl (0.04%) Gold 11.0 272 160 0.074
8.6 52 10 0.025 8.6 52 10 0.025
P-PPV Pl(02%) 金 12.0 28.8 7756 3.430 P-PPV Pl (02%) Gold 12.0 28.8 7756 3.430
9.4 2061 5.567 参照例 9.4 2061 5.567 Reference example
P-PPV 4.8 52 3952 9.64 P-PPV 4.8 52 3952 9.64
3.7 0.5 475 11.75 3.7 0.5 475 11.75
P-PPV 铝 9.0 18.1 312 022 P-PPV aluminum 9.0 18.1 312 022
7.7 52 65 0.16 7.7 52 65 0.16
由此例之结果可以充分说明对发绿光的 P-PPV常规器件，当直接用铝或金等高功函数作阴极时器 件的量子效率比相应低功函数阴极钡的器件低得多。但当用 P1置于发光层与高功函数金属之间时， 器件的 效率达到 相应低功函数金属钡作阴极的器件。 The results of this example can fully explain that for conventional green P-PPV devices, the quantum efficiency of the device when directly using a high work function such as aluminum or gold as the cathode is much lower than that of the corresponding low work function cathode barium device. However, when P1 is placed between the light-emitting layer and the high work function metal, the efficiency of the device reaches a device with a corresponding low work function metal barium as the cathode.
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替换页（细则第 26条）
实施例 15 Replacement page (Article 26) Example 15
重复例 2将聚合物发光层置换为; ¾光的聚笏材料 PFO, 在 层上旋转涂敷 40nm的 PW层， 改善空穴的注入，其它 不变。实验结果总结于表 3。图 6中比 光的聚笏 PF0用金作阴极时 有无 P1层的器件的发光 ¾¾¾发 量子效率。 Repeat Example 2 to replace the polymer light-emitting layer with; ¾ light Pho material PFO, spin-coated a 40nm PW layer on the layer, to improve the injection of holes, the others remain unchanged. The experimental results are summarized in Table 3. In Figure 6, the light-emitting poly PF0 uses the gold as the cathode and the light emission of the device with or without the P1 layer ¾ ¾ ¾ Quantum efficiency.
表 3 的聚芴材料 (PP0)用 P1作为电子 ¾Λ层的器件的电 ¾ ^性能,器件结构为 ITO PEDOT P ADS^g/Pl/Al (Au) Table 3 shows the electrical properties of the device using PP1 as the electron ¾Λ layer. The device structure is ITO PEDOT P ADS ^ g / Pl / Al (Au)
电子 ¾Λ层 阴极 电流 m 夕 效率 Electron ¾Λ layer cathode current m xi efficiency
(備） («¾) 平方米） (%) (Prepared) («¾) square meters) (%)
PFO Pl(0.04%) 铝 13.0 163 179 029 PFO Pl (0.04%) Aluminum 13.0 163 179 029
112 52 49 025 112 52 49 025
PFO Pl(02%) 铝 9.0 4.7 323 1.77 PFO Pl (02%) Aluminum 9.0 4.7 323 1.77
7.7 0.4 31 230 7.7 0.4 31 230
PFO Pl(0.04%) 金 13.0 122 17 0.04 PFO Pl (0.04%) Gold 13.0 122 17 0.04
11.7 5.0 7 0.04 11.7 5.0 7 0.04
PFO Pl(02%) 金 11.8 53 403 1575 PFO Pl (02%) Gold 11.8 53 403 1575
11.5 1.0 127 3.466 参照例 11.5 1.0 127 3.466 Reference example
PFO - f!/铝 10.1 4.9 729 390 PFO-f! / Aluminum 10.1 4.9 729 390
8.6 1.4 250 4.62 8.6 1.4 250 4.62
PFO - 铝 15.0 8.6 14 0.04 PFO-Aluminum 15.0 8.6 14 0.04
14.4 52 2 0.Q2 14.4 52 2 0.Q2
ΡΡΌ - 金 26.0 14.1 1 0.001 ΡΡΌ-Gold 26.0 14.1 1 0.001
24.4 4.8 0.5 0.0Q2 24.4 4.8 0.5 0.0Q2
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替换页（细则第 26条)
由此例之结果可以充 明对 «光的 pro常规器件， 当直接用铝或金等高功函数作阴极时器 件的量子效率比相应低功函数阴极钡的器 (氐得多。但当用 PI置于发光层与高功函数金属之间时， 器件的量子效率达到 相应低功函数金属钡作阴极的器件。 实施例 16 Replacement page (Article 26) The results of this example can clearly show that for conventional devices of «light pro, when the high work function such as aluminum or gold is directly used as the cathode, the device's quantum efficiency is much higher than the corresponding low work function cathode barium device (but much more When PI is placed between the light-emitting layer and the high work function metal, the quantum efficiency of the device reaches a device with a corresponding low work function metal barium as the cathode. Example 16
重复例 2将电子注入层置换为侧链带有磺 ¾基功能团的聚合物 (P2)， 其它 牛不变。 实验结 果总结于表 4。 图 7中比较发红光的 MEH-PPV用铝作阴极时， 有无 P1层的器件的发光亮度及发光外 量子效率。 Example 2 was repeated. The electron injection layer was replaced with a polymer (P2) having a sulfo ¾ group functional group in the side chain, and the others were unchanged. The experimental results are summarized in Table 4. In Figure 7, when the red-emitting MEH-PPV uses aluminum as the cathode, the light emission brightness and external light emission quantum efficiency of the device with or without the P1 layer are compared.
表 4基于红光材料聚 [2—甲氧基 (5- (2' -BSTl-1, 4—苯乙炔） ] (Mffi-PPV), 以侧链带 ¾1»8¾能团 的聚^物， PF-SOWaO¾作为电子 层的器件的电¾¾光性能， 器件结构为 ITO/PEDOT/tePPV K/M Table 4 Based on the red light material poly [2-methoxy (5- (2'-BSTl-1, 4-phenylacetylene)] (Mffi-PPV), a polymer with a side chain with ¾1 »8¾ energy group, Electrical performance of PF-SOWaO¾ as an electronic layer, the device structure is ITO / PEDOT / tePPV K / M
发光层 电子 ax层 阴极 电压 电流 m& 外: IT效率 Light emitting layer electron ax layer cathode voltage current m & out: IT efficiency
(伏特） 獰安） （敏平方米） （％) (Volts) Zhao'an) (Min square meters) (%)
MEHPPV Ε2(02%) 铝 4 4.6 123 0.71 参照例 MEHPPV Ε2 (02%) Aluminum 4 4.6 123 0.71 Reference example
MEHPPV - 铝 5.5 5.1 7 0.038 MEHPPV-Aluminum 5.5 5.1 7 0.038
由此例之结果可以充分说明当用侧链带有磺隱基功能团的聚合物 PF-SWa(P2) 置于发光层与 高功函数金属铝之间时， 器件的量子效率大大超过直接用铝作阴极的器件。 The results of this example can fully explain that when the polymer PF-SWa (P2) with a sulfo hidden functional group in the side chain is placed between the light-emitting layer and the high work function metal aluminum, the quantum efficiency of the device greatly exceeds the direct use Aluminum as the cathode device.
20 20
替换页（细则第 26条)
实施例 17 Replacement page (Article 26) Example 17
重复例 2将电子注入层置换为含有窄带隙的三组分共聚物 (窄带隙的单体苯并噻二 (P3) 作为 电子注入层， 其它餅不变。 实验结果总结于表 5。 Example 2 was repeated. The electron injection layer was replaced with a three-component copolymer containing a narrow band gap (narrow band gap monomer benzothiadi (P3) as the electron injection layer. The other cakes were unchanged. The experimental results are summarized in Table 5.
表 5基于红光材料聚 [2—甲氧基 (5- (2， 一乙基）一己基氧一 1, 4一苯乙炔） ] (Mffi-PPV), 以窄带隙的单体苯并噻二唑 的三元共聚合物 (ί¾作为电 ΐ¾λ层的器件的电致^ ¾性能， 器件结构为 ITO/PEDOT/MEHPPV/P3/A1 m 电子 ^层 阴极 电压 电流 ^ 夕卜 效率 Table 5 Based on the red light material poly [2-methoxy (5- (2, monoethyl) -hexyloxy-1, 4-phenylphenylacetylene)] (Mffi-PPV), with a narrow band gap monomer benzothia The ternary copolymer of a diazole (e.g., the electroluminescence properties of a device as an electric layer), the device structure is ITO / PEDOT / MEHPPV / P3 / A1 m electrons, cathode voltage, current, and efficiency.
(伏特） 安） 薪方米） (%) (Volts) Ann) Salary meters (%)
MEHPPV P3(02%) 铝 8.0 34.1 3004 229 参照例 MEHPPV P3 (02%) Aluminum 8.0 34.1 3004 229 Reference example
MEHPPV - 铝 7.0 32.5 157 MEHPPV-Aluminum 7.0 32.5 157
MEHPPV - 柳铝 7.0 32.7 2645 由此例之结果可以充 明当用含有窄带隙的单体苯并噻二唑的三元共聚合物 (P3)置于发光层 与高功函数金属铝之间时， 器件的量子效率大大 ^¾接用铝作阴极的器件，其量子效率超过用低 功函数金属钡作阴极的器件。 MEHPPV-Willow Aluminum 7.0 32.7 2645 The results of this example are clear when a terpolymer (P3) containing a narrow band gap monomer benzothiadiazole is placed between the light emitting layer and the high work function metal aluminum The quantum efficiency of the device is significantly higher than that of a device using aluminum as a cathode, and its quantum efficiency exceeds that of a device using low work function metal barium as a cathode.
21 twenty one
替换页（细则第 26条)
Replacement page (Article 26)
Claims
1、一种有机 /高^ f发光二极管， 由阴极 (1)、 发光层 (2)、 空穴注入层 (3)、 阳极 (4)、衬底 (5) 依次层叠构成， 其特征在于在阴极 (1)与发光层 (2)之间设一电子注入层 (6)， 所述电子注入层采用含 有极性基团或离子性基团的极性单元共轭聚合物。 1. An organic / high light emitting diode, which is composed of a cathode (1), a light emitting layer (2), a hole injection layer (3), an anode (4), and a substrate (5). An electron injection layer (6) is provided between the cathode (1) and the light emitting layer (2), and the electron injection layer uses a polar unit conjugated polymer containing a polar group or an ionic group.
2、根据权利要求 1戶 M的有 fl/高^ P发光二极管， 其特征在于将发光层 (2)与电子注入层⑥ 合并为一层， 该层采用含有极性基团或离子性基团的极性单元共轭聚合物。 2. The light emitting diode with fl / high ^ P according to claim 1, characterized in that the light-emitting layer (2) and the electron injection layer (6) are combined into one layer, and the layer includes a polar group or an ionic group. Conjugated polymer of polar units.
3、根据权利要求 1或 2纖的有 1/高 发光二极管， 期寺征在于戶 M含有极性基团或离子 性基团的极性单元共轭聚合物具有如下结构：
3. The 1 / high light emitting diode according to claim 1 or 2, wherein the polar unit conjugated polymer containing a polar group or an ionic group in the M has the following structure:
其中 r¾ =1, 2, 3···. ;¾ r¾=0, 1, 2 ； Where r¾ = 1, 2, 3 ···; ¾ r¾ = 0, 1, 2;
其中 A为含有极性基团或离子性基团的极性组分， 具有如下其中一种或多种结构的组合: Where A is a polar component containing a polar group or an ionic group, and has a combination of one or more of the following structures:
m
， 为带有胺基、 安盐基、腈基、羧基、磺酸基、憐酸 ¾¾中一个 或多个侧链； n=l, 2, 3……； m , With one or more side chains of an amine group, an ammonium group, a nitrile group, a carboxyl group, a sulfonic acid group, and a phosphoric acid; n = 1, 2, 3, ...;
¾x寸苯乙炔：
ι¾， 为带有胺基、 安盐基、腈基、羧基、磺酸基、 m 中一个或多个的侧链； n=l, 2, 3……； ¾x inch phenylacetylene: ι¾, which is a side chain with one or more of amine group, hydrazine group, nitrile group, carboxyl group, sulfonic acid group, and m; n = l, 2, 3 ...;
22 twenty two
替换页（细则第 26条）
聚 SP删寸苯：
其中 I¾， 为带有驢、 安盐基、腈基、羧基、磺酸基、 磷酸 ¾¾中一个或多个的侧链； n=l, 2， 3……； Replacement page (Article 26) Poly SP deleted inch benzene: Where I¾ is a side chain with one or more of donkey, hydrazine, nitrile, carboxyl, sulfonic acid, and ¾¾; n = l, 2, 3 ...;
慰寸苯撑乙炔：
11， 为带有胺基、 安盐基、腈基、羧基、磺酸基、磷酸基 其中一个或多个的侧链； n=l, 2, 3……； Comfort inch phenylene acetylene: 11, is a side chain with one or more of an amine group, a salt group, a nitrile group, a carboxyl group, a sulfonic acid group, and a phosphate group; n = 1, 2, 3, ...;
聚咔唑:
Rl为带有胺基、 安盐基、腈基、羧基、磺酸基、磷酸 «中一个 或多个的侧链； n=l, 2, 3……； 其中 B为不含有极性或离子性基团的组分， 具有如下的一种或几种结构：
其中 !¾， 为11， 的烧基； n-1, 2, 3
2, 3 Polycarbazole: Rl is a side chain with one or more of amine, sulfonyl, nitrile, carboxyl, sulfonic, and phosphoric acid «n = 1, 2, 3 ...; where B is free of polarity or ions The component of the sex group has one or more of the following structures: Where! ¾ is a radical of 11, and n-1, 2, 3 twenty three
救寸苯乙炔：
的烷氧基； n=l, 2， 3· Rescue phenylacetylene: Alkoxy; n = l, 2, 3 ·
聚 SPIR0"对苯: 3· Poly SPIR0 "p-benzene: 3 ·
慰寸苯撑乙炔：
2, 3· Comfort inch phenylene acetylene: twenty three·
23 twenty three
替换页（细则第 26条)
聚昨唑： L R3 」 其中1¾为¾ 的院基； n=1， 2, 3· 其中 C为扭可含有硫， 氧,氮， 硒等元素其中一种或者多种的杂环。 Replacement page (Article 26) Polyesterazole: LR 3 ”where 1¾ is a ¾ base; n = 1 , 2, 3 · where C is a heterocyclic ring that may contain one or more of sulfur, oxygen, nitrogen, selenium and other elements.
4、根据权利要求 1或 2所述的有 /高 ^^发光二极管， 其特征在于所述阴 用功函数大于 或等于 3.6电子伏特的髙功函数金属。 The light emitting diode according to claim 1 or 2, characterized in that said negative work function metal has a work function function of greater than or equal to 3.6 electron volts.
5、根据权利要求 4所述的有 iH/高^1发光二极管， 其特征在于所述电子注入层由在有机 ί ί] 中的溶液通过旋转涂敷， 喷墨， 印刷等溶液藤的方式涂敷于发光层上形成， 其厚度介于 0.3至 30 纳米。 5. The iH / high ^ 1 light emitting diode according to claim 4, wherein the electron injection layer is coated with a solution in an organic solution by spin coating, inkjet, printing, or other solutions. It is formed on the light-emitting layer, and the thickness is between 0.3 and 30 nanometers.
6、根据权利要求 5所述的有机 /高肝发光二极管， 其特征在于所述阴丰翻功函数大于或等 于 3.6电子伏特的高功函数金属。 6. The organic / high-liver light-emitting diode according to claim 5, characterized in that the high-work function metal having a yin-feng conversion work function greater than or equal to 3.6 electron volts.
7、根据权利要求 5所述的有机 /高 发光二极管， 其特征在于所述高功函数金属是金、 铝、 铜、银、铟、镍、 铅、 锡、碳、 石墨或它们的合金。 7. The organic / high light emitting diode according to claim 5, wherein the high work function metal is gold, aluminum, copper, silver, indium, nickel, lead, tin, carbon, graphite, or an alloy thereof.
8、根据权利要求 6所述的有ίΙ/高肝发光二极管， 其特征在于所述髙功函数金属是金， 铝， 铜， 银， 铟， 镍， 铅， 锡， 碳， 石墨， 或其合金。 8. The light emitting diode according to claim 6, wherein the metal of the work function is gold, aluminum, copper, silver, indium, nickel, lead, tin, carbon, graphite, or an alloy thereof .
9、根据权利要求 7所述的有机 /高分子发光二极管， 其特征在所述发光层为有机高^ f发光材 料或者是这些发光材料发光基团被取代的慰寸苯， 聚芴，聚 SPIRO对苯，梯形! ^寸苯 (ladderfPP)， 辦苯撑乙炔的共聚物。 9. The organic / polymer light emitting diode according to claim 7, characterized in that the light emitting layer is an organic high light emitting material or a light emitting group in which the light emitting group is replaced by benzene, polyfluorene, polySPIRO To benzene, trapezoid! ^ Inch benzene (ladderfPP), a copolymer of phenylene acetylene.
10、根据权利要求 8所述的有机 /高 发光二极管， 其特征在所述发光层为有机高肝发光材 料或者是这些发光材料发光基赚取代的舰苯， 聚芴， 聚 SPIRO"对苯， 梯形 (寸苯 (ladderfPP) , 辦苯撑乙炔的共聚物。 10. The organic / high light-emitting diode according to claim 8, characterized in that the light-emitting layer is an organic high-hepatic light-emitting material or a light-emitting group of these light-emitting materials, which is substituted by benzene, polyfluorene, poly-SPIRO, p-benzene, Ladder (ladderfPP), a copolymer of phenylene acetylene.
24 twenty four
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| WO2006113184A1 (en) * | 2005-04-15 | 2006-10-26 | General Electric Company | Modified electrodes using functional organic materials and electronic devices therefrom |
| US8741442B2 (en) | 2005-04-15 | 2014-06-03 | General Electric Company | Modified electrodes using functional organic materials and electronic devices therefrom |
| US9455408B2 (en) | 2009-09-30 | 2016-09-27 | Sumitomo Chemical Company, Limited | Layered structure, polymer, electroluminescent device, and photoelectric conversion device |
| EP2597696A4 (en) * | 2010-07-21 | 2018-01-10 | Sumitomo Chemical Company Limited | Organic el element |
| US9306170B2 (en) | 2011-03-28 | 2016-04-05 | Sumitomo Chemical Company, Limited | Electronic device and polymer compound |
| US9306169B2 (en) | 2011-03-28 | 2016-04-05 | Sumitomo Chemical Company, Limited | Electronic device, polymer compound, organic compound, and method of producing polymer compound |
| US9601696B2 (en) | 2011-03-28 | 2017-03-21 | Sumitomo Chemical Company, Limited | Electroluminescent composition and electric device with high brightness |
| WO2013167224A1 (en) | 2012-05-10 | 2013-11-14 | Merck Patent Gmbh | Formulation comprising ionic organic compounds for use in electron transport layers |
| CN106876611A (en) * | 2016-12-22 | 2017-06-20 | 成都新柯力化工科技有限公司 | A kind of preparation method and application of the composite blue light material shown for OLED |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100490206C (en) | 2009-05-20 |
| CN1555103A (en) | 2004-12-15 |
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