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WO2014205967A1 - Matériau d'injection de trous pour dispositif électroluminescent organique, et procédé de préparation et utilisation associés - Google Patents

Matériau d'injection de trous pour dispositif électroluminescent organique, et procédé de préparation et utilisation associés Download PDF

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Publication number
WO2014205967A1
WO2014205967A1 PCT/CN2013/085774 CN2013085774W WO2014205967A1 WO 2014205967 A1 WO2014205967 A1 WO 2014205967A1 CN 2013085774 W CN2013085774 W CN 2013085774W WO 2014205967 A1 WO2014205967 A1 WO 2014205967A1
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WIPO (PCT)
Prior art keywords
hole injection
phthalocyanine
injection material
organic
film
Prior art date
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Ceased
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PCT/CN2013/085774
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English (en)
Chinese (zh)
Inventor
许宗祥
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Southwest University of Science and Technology
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Southwest University of Science and Technology
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Publication of WO2014205967A1 publication Critical patent/WO2014205967A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
    • 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

Definitions

  • the present invention relates to a material for an organic electroluminescence device, and more particularly to a hole injecting material for a high performance organic electroluminescent device.
  • the present invention also relates to a method of preparing the hole injecting material and its use in an organic electroluminescent device. Background technique
  • the organic electroluminescent process is completed by the following steps: (1) injection of carriers, electrons and holes are injected from the cathode and the anode to the inside of the electrode, respectively Inter-organic functional thin film layer; (2) carrier migration, carriers migrate from electron transport layer ETL and hole transport layer HTL to light-emitting layer ELL, respectively; (3) exciton generation, holes and electrons The luminescent layer ELL meets and binds to each other to generate excitons. (4) The emission of photons, the excited state energy is deactivated by radiation, generating photons and releasing light energy.
  • the OLED device material can be distinguished as the device anode material indium tin oxide glass ⁇ ), hole injection layer (HID, hole transport layer (HTL), light-emitting layer (EML) , electron transport layer (ETL), electron injection layer (EIL), cathode material metal electrode, etc.
  • HID hole injection layer
  • HTL hole transport layer
  • EML electron transport layer
  • EIL electron injection layer
  • cathode material metal electrode etc.
  • the performance and quality of these materials are directly related to the performance and lifetime of OLED devices.
  • the efficiency of OLED display devices depends first and foremost on whether they can be effective. Charge injection, therefore, hole injection materials are essential. Through research, the development of new high-efficiency organic hole injection materials can increase carrier injection, improve carrier balance and increase the probability of exciton formation and recombination. OLED device An effective way of efficiency and longevity.
  • the hole injection materials reported at home and abroad are mainly divided into two different types of materials: vapor deposition and liquid phase spin coating.
  • the hole injecting materials prepared by vapor deposition are mainly transition metal oxides and organic small molecular materials
  • the hole injecting materials prepared by liquid phase spin coating are mainly high molecular polymers and soluble organic small molecular materials. Transition metal oxides have excellent electronic properties and high light transmittance in the visible region.
  • Current research and development focuses on molybdenum oxide (Mo0 3 ), vanadium oxide (V 2 0 5 ), and tungsten oxide (W0 3 ), mainly through magnetic
  • the controlled sputtering method was performed by evaporation.
  • the Ma Dongge Research Group of the Changchun Institute of Applied Physical Chemistry reported that a green OLED using Mo0 3 as a hole injection layer achieves low voltage operation (2.4 V) and the device lifetime reaches 50,000 hours; while the small molecule material passes vacuum heat.
  • the hole injection layer was prepared by an evaporation method, and the main research materials were 2T-NATA and metal phthalocyanine.
  • Dr. Deng Qingyun the father of OLED, prepared a light-emitting device using copper phthalocyanine as a hole injection material, which improved the hole injection stability of the device, thereby improving the luminous efficiency and lifetime of the device.
  • WO2012058788A1 discloses a phthalocyanine/polymer nanocomposite photoelectric ink which, by thiol substitution of phthalocyanine (Pc), can achieve self-assembly of Pc, thereby improving energy conversion efficiency.
  • PEDOT is a polymer of EDOT (3,4-ethylenedioxythiophene monomer), PSS is a polystyrene sulfonate, as a water-soluble polymer material, PEDOT: PSS is used as a hole buffer layer for organic light-emitting devices and The hole injecting layer can reduce the turn-on voltage, and the luminous flux is widely concerned.
  • the organic functional layer in the OLED is very sensitive to water and oxygen, it easily reacts with the infiltrated water vapor or oxygen to form a black spot that does not emit light.
  • PEDOT: PSS residual water in the later stages of device preparation can easily affect the performance of the finished device.
  • the work function value of the anode ITO is generally (4.5-4.7 ev), and the HOMO level of the hole transport material is about 5.3 ev.
  • the difference between the two is relatively large, which is not conducive to the effective injection of holes, resulting in devices.
  • ITO film is the substrate (adsorption, internal stress and crystallinity) of organic film deposition. Since the rough surface will be disadvantageous for cohesion between the organic molecules to form crystals, the rough surface is liable to form an organic film of an amorphous structure.
  • the appearance of crystalline organic matter will increase the possibility of electron collision with the lattice, which will reduce the luminous efficiency and energy efficiency of the OLED device; considering the case of applying current to the OLED, the rough surface will affect the OLED.
  • Internal electric field distribution For OLED devices with a rough tantalum surface, the peak of the ITO surface will result in a local high electric field, which will dissociate the excitons into positive and negative electrodes, resulting in a decrease in luminescence intensity, and a high electric field will accelerate the deterioration of the organic material.
  • the stability of the OLED is lowered; therefore, it is necessary to modify the surface of the anode ITO, develop an organic soluble metal phthalocyanine, form a film by a low-temperature liquid phase process, and introduce a hole injection layer between the ITO and the hole transport layer to improve The contact between the ITO and the organic layer and the ability to inject holes, while making the surface of the ITO more flat, reducing the hole injection barrier and improving the efficiency of the device; at the same time, the hole injection layer can effectively prevent In and 0 from the anode material. ITO diffuses into the organic layer, improving the life of the device
  • the object of the present invention is to overcome the problem that excessive crystallization of a conventional phthalocyanine molecule during film formation leads to a film roughness being too large.
  • OLED organic electroluminescent device
  • n 2, 4 or 6
  • M is hydrogen, copper, zinc, nickel or palladium.
  • the invention also provides a preparation method of the hole injection material, which comprises the following preparation steps
  • the present invention also provides an organic electroluminescence device using the above hole injecting material.
  • the present invention also provides the use of the above hole injecting material in the field of organic electroluminescence.
  • the invention thiol-substituted the ⁇ -position of the metal phthalocyanine, and the synthesis and purification are simple and easy to be industrialized and scaled. It can not only improve the organic solubility of the material, but also achieve the solution film formation at room temperature, reduce the energy consumption of preparation, and enhance the ⁇ -conjugated system accumulation of the material molecules after film formation by modifying the interaction force between the ruthenium groups.
  • a- Partial isomers are formed during the synthesis of tetradecyl-substituted phthalocyanines, thus preventing the disadvantage that excessive crystallization of conventional phthalocyanine molecules during film formation leads to too large film roughness.
  • (X-tetradecyl-substituted copper phthalocyanine forms a flat and dense film, rather than a granular crystalline morphology, which is beneficial to reduce the surface roughness of the ITO glass substrate;
  • the cyanine material can reduce the difference between the HOMO level of the hole transporting material and the ITO work function, and improve the hole injection efficiency.
  • the phthalocyanine layer itself facilitates carrier injection, reduces interface resistance, and thus reduces interface heat generation, phthalocyanine layer.
  • the thermal stability is very good, and the deformation of the functional layer film due to the heat generated by the interface resistance of the ITO and the organic layer during the operation of the device can be reduced, so that the life of the device can be improved.
  • Figure 1 is a schematic diagram of the operation of an organic electroluminescent device.
  • Figure 2 shows the molecular structure of the ⁇ -position-substituted metal phthalocyanine ( ⁇ -RMPc).
  • Figure 3 is a SEM characterization of (a) copper phthalocyanine; (b) a-tetraethyl copper phthalocyanine.
  • Figure 4 shows the OLED electronic energy level diagram.
  • Figure 5 is a roadmap for the synthesis of phthalocyanine molecules.
  • Figure 6 is a UV-visible absorption spectrum of a 4-ethyl copper phthalocyanine chloroform solution.
  • Figure 7 is a schematic diagram of the OLED structure and the molecular structure of the OLED material. Concrete implementation
  • Example 3 This was carried out in the same manner as in Example 1 except that zinc chloride was used instead of copper chloride.
  • Example 4 This was carried out in the same manner as in Example 1 except that nickel chloride was used instead of copper chloride.
  • ITO is used as the anode of the device
  • TPD is the hole transporting material
  • Alq 3 is the electron transporting material
  • LiF/Al is the cathode.
  • the standard device ITO/TPD/Alq 3 /LiF/Al is prepared by vacuum evaporation, respectively.
  • the phthalocyanine is a hole injecting material
  • a solution is prepared using dichloromethane as a solvent
  • a hole injecting layer is prepared by a spin coating method between the anode ITO and the hole input material TPD
  • a light emitting device ITO/a is prepared in a nitrogen glove box.
  • -RMPc/TPD/Alq 3 /LiF/Al see Figure 7 and packaged and tested.
  • the test result uses a-RMPc as the hole injection layer, and the brightness of the OLED device is increased by more than 30%, and the lifetime is increased by 50%.
  • the invention thiol-substituting the a-position of the metal phthalocyanine, and the synthesis and purification are simple and easy to be industrialized scale production. Not only can improve the organic solubility of materials, but also achieve a solution process at room temperature.
  • Membrane which reduces the energy consumption of preparation, and can enhance the carrier ⁇ -conjugated system accumulation after film formation by modifying the interaction force between the ruthenium groups, and improve the carrier mobility of the material; (X-tetradecyl substitution) Partial isomers are formed during the synthesis of phthalocyanine, thus preventing the excessive crystallization of conventional phthalocyanine molecules during film formation, resulting in a film roughness that is too large.
  • a-tetramethyl Substituting copper phthalocyanine to form a flat and dense film, rather than a granular crystalline morphology is beneficial to reduce the surface roughness of the bismuth glass substrate; phthalocyanine material can reduce the hole transport material HOMO level The difference in energy level from the ITO work function (see Figure 4) improves the hole injection efficiency.
  • the phthalocyanine layer itself facilitates carrier injection, reduces interface resistance, and thus reduces interface heat generation.
  • the phthalocyanine layer has good thermal stability. It can reduce the deformation of the functional layer film due to the heat generated by the interface resistance of the ITO and the organic layer during the operation of the device, so that the lifetime of the device can be improved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne un matériau d'injection de trous destiné à un dispositif électroluminescent organique. Au cours du procédé de synthèse du matériau, un groupe alcane à chaîne linéaire est introduit en position α de la structure cyclique phtalocyanine classique, et des ions substituants métalliques différents sont utilisés au centre du noyau phtalocyanine. La substitution par un alkyle est réalisée en position α de la phtalocyanine métallique, et la synthèse et la purification associées sont simples et pratiques, et faciles pour la production en masse à l'échelle industrielle. De plus, en modifiant les forces d'interaction entre groupes alkyle, l'encombrement du système π-conjugué des molécules du matériau après formation du film est amélioré, et la mobilité des porteurs de charge du matériau est accrue ; certains des isomères peuvent être formés pendant le procédé de synthèse de la phtalocyanine substituée par un tétra-alkyle en α, de sorte à pouvoir éliminer les défauts de rugosité extrêmement élevée du film mince provoqués par une cristallisation excessive pendant le procédé de formation du film de molécules de phtalocyanine classique.
PCT/CN2013/085774 2013-06-26 2013-10-23 Matériau d'injection de trous pour dispositif électroluminescent organique, et procédé de préparation et utilisation associés Ceased WO2014205967A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310258400.8 2013-06-26
CN2013102584008A CN103319490A (zh) 2013-06-26 2013-06-26 一种有机电致发光器件空穴注入材料、其制备方法及应用

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WO2014205967A1 true WO2014205967A1 (fr) 2014-12-31

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WO (1) WO2014205967A1 (fr)

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CN103319490A (zh) * 2013-06-26 2013-09-25 南方科技大学 一种有机电致发光器件空穴注入材料、其制备方法及应用
CN103500801B (zh) * 2013-10-12 2016-08-24 上海和辉光电有限公司 顶发光蓝光有机发光二极管及其制造方法
CN105330667B (zh) * 2015-12-07 2017-12-19 南方科技大学 金属酞菁凝胶及其应用
KR20170114799A (ko) * 2016-04-06 2017-10-16 현대자동차주식회사 내열성이 높은 자동차용 페로브스카이트 태양전지용 정공전달물질, 이를 포함하는 페로브스카이트 태양전지 및 이의 제조방법
CN109659569B (zh) * 2019-01-30 2020-10-16 南方科技大学 金属酞菁类分子前驱体构筑单位点电催化剂的方法及应用
CN109867682B (zh) * 2019-03-01 2020-05-19 南方科技大学 一种α位四丙基取代金属酞菁及其制备方法、一种钙钛矿太阳能电池及其制备方法
CN110078739B (zh) * 2019-05-13 2020-10-30 南方科技大学 一种空穴传输材料及其制备方法、钙钛矿太阳能电池
CN110828682A (zh) * 2019-10-16 2020-02-21 南方科技大学 有机发光二极管及其制备方法和显示面板
CN111048692A (zh) * 2019-12-05 2020-04-21 南方科技大学 聚合物发光二极管及其制备方法
WO2022056886A1 (fr) * 2020-09-19 2022-03-24 Huawei Technologies Co., Ltd. Écran électroluminescent organique

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