WO2024060203A1 - Matériau d'injection de trous organiques et utilisation - Google Patents

Matériau d'injection de trous organiques et utilisation Download PDF

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Publication number
WO2024060203A1
WO2024060203A1 PCT/CN2022/120874 CN2022120874W WO2024060203A1 WO 2024060203 A1 WO2024060203 A1 WO 2024060203A1 CN 2022120874 W CN2022120874 W CN 2022120874W WO 2024060203 A1 WO2024060203 A1 WO 2024060203A1
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WIPO (PCT)
Prior art keywords
hole injection
organic
chloroform
molecular formula
injection material
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PCT/CN2022/120874
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English (en)
Chinese (zh)
Inventor
孟鸿
蔡瑜
陆科
闫朝一
贺耀武
胡钊
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北京大学深圳研究生院
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Application filed by 北京大学深圳研究生院 filed Critical 北京大学深圳研究生院
Priority to PCT/CN2022/120874 priority Critical patent/WO2024060203A1/fr
Publication of WO2024060203A1 publication Critical patent/WO2024060203A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the invention relates to the field of organic light emitting, and in particular to an organic hole injection material and its application.
  • OLEDs Organic Light-emitting Diodes
  • the hole injection layer serves as the key material connecting the anode and the organic functional layer. It can lower the barrier for hole injection from the anode, allowing holes to be efficiently injected from the anode into the OLED device. Therefore, when selecting the hole injection layer material, it is necessary to consider the matching of the material energy level and the anode material.
  • the function of the injection layer is to make a good match between the work function of the anode and the HOMO of the hole transport layer material, so that holes can flow smoothly from the electrode to the transport layer.
  • the luminescent material The highest occupied orbital energy level is close to the work function of the anode, lowering the hole injection energy barrier.
  • a hole injection layer is usually added between the anode and the hole transport layer, mainly because the energy barrier between the anode and the hole transport layer is large, which will cause the driving voltage of the component to increase, indirectly causing The life of the component is shortened, so a layer of material whose HOMO energy level is between the anode and the hole transport layer is added to improve the efficiency between the hole injection and the hole transport layer.
  • hole injection materials used in optoelectronic devices can be divided into two categories: inorganic hole injection materials and organic hole injection materials.
  • Inorganic hole injection materials easily react with organic layers at high temperatures, and the high evaporation temperature of inorganic hole injection materials is not conducive to the preparation of organic optoelectronic devices.
  • Organic hole injection materials can be divided into small molecule hole injection materials and polymer hole injection materials. Polymer hole injection materials are also very limited due to their purity and the inability to prepare devices by evaporation. Small molecule organic hole injection materials can produce very high-purity materials and can produce high-quality devices through evaporation methods. However, there are relatively few small molecules with suitable HOMO and LUMO energy levels, and the selection range is small. Therefore, it is necessary to develop new suitable organic small molecule hole injection materials. Developing suitable hole injection materials plays an important role in improving the device performance of OLEDs.
  • the present invention provides an organic hole injection material and its application.
  • an organic hole injection material is provided, the general structural formula of which is as follows:
  • X, Y, and Z are each independently selected from C, O, CO, S, Se, SO, SeO, SO 2 or SeO 2 ;
  • At least one of R 1 , R 2 , R 3 and R 4 is selected from F, CN, or The remainder is hydrogen.
  • Y or Z are different, and one of Y or Z is C.
  • At least two of R 1 , R 2 , R 3 and R 4 are selected from F, CN, or The same or different from each other.
  • some or all of the hydrogens in the molecular formula are replaced by deuterium.
  • the organic hole injection material is represented by any one of the following compounds:
  • the invention also provides an organic light-emitting device based on a double five-membered ring derivative substituted by a fluorine atom or a cyano group or a pentafluorophenyl group as a hole injection layer material.
  • the double five-membered ring is selected from thiophene, furan or selenophene double five-membered ring groups.
  • the specific structure of the device is a transparent substrate, anode, hole injection layer, hole transport layer, electron blocking layer, light emitting layer, electron transport layer and cathode.
  • the transparent substrate can be glass or plastic.
  • Anode materials are inorganic materials such as indium tin oxide, zinc oxide, tin zinc oxide, etc.;
  • the material of the hole injection layer can be any one of the above general formulas
  • the hole transport layer material can be any of the following:
  • the electron blocking layer material can be any organic compound.
  • the guest material in the light emitting layer can be BPH.
  • the hole blocking layer material can be any of the following:
  • the electron transport layer material can be any of the following:
  • the electron injection layer can be lithium fluoride, Liq, etc.
  • the cathode material is metal aluminum, magnesium silver alloy, etc.
  • the present invention also provides a perovskite solar cell, which includes a cathode, an anode and each organic layer; wherein, the hole injection layer uses any one of the aforementioned organic hole injection materials.
  • the hole injection material provided by the present invention is a double five-membered ring derivative substituted by an electron-deficient group.
  • the double five-membered ring includes but is not limited to thiophene, furan or selenium phenol double five-membered ring group. .
  • this type of material is relatively simple and is conducive to large-scale production; the HOMO and LUMO energy level structure of the material is suitable, which is conducive to the injection of carriers; the material has substituents and five-membered rings as the core, which is conducive to the transfer of carriers in the device Medium transmission; the material has a high LUMO/HOMO energy level, which is beneficial to transporting holes from the anode ITO to the hole transport layer.
  • the material has a suitable energy level structure and can be used as a hole injection layer material for organic light-emitting devices.
  • the organic light-emitting diode prepared by the present invention using the above hole injection layer material has high luminous efficiency and device life. When applied to perovskite solar cells, it can improve the photoelectric conversion efficiency and has high commercial value.
  • FIG1 is a schematic diagram of the structure of an organic light-emitting device according to an embodiment of the present invention.
  • Figure 2 is a schematic structural diagram of a perovskite solar cell using one embodiment of the present invention.
  • the compounds whose synthesis methods are not mentioned in the present invention are all raw material products obtained through commercial channels.
  • the solvents and reagents used in the present invention can be purchased from the domestic chemical market. In addition, those skilled in the art can also synthesize them through known methods.
  • the synthesis method of the compound specifically includes the following steps:
  • the synthetic route of molecular formula 100 is as follows:
  • the synthesis method of the compound specifically comprises the following steps:
  • the synthesis method of the compound specifically includes the following steps:
  • the synthesis method of the compound specifically includes the following steps:
  • the synthesis method of the compound specifically includes the following steps:
  • the synthesis method of the compound specifically comprises the following steps:
  • the synthesis method of the compound specifically includes the following steps:
  • the synthesis method of the compound specifically includes the following steps:
  • the synthesis method of the compound specifically includes the following steps:
  • the synthesis method of the compound specifically comprises the following steps:
  • the synthesis method of the compound specifically includes the following steps:
  • the toluene solution was then transferred to a solution of pentafluorobromobenzene (6 mL, 50 mmol) and tetrakis(triphenylphosphine)palladium (2.3 g, 1.9 mmol) in toluene (40 mL) and the mixture was refluxed at 140°C for 2 days. After cooling to room temperature, the mixture was filtered through a celite column with toluene. Finally, the toluene solutions were combined and concentrated, and recrystallized from chloroform to obtain the compound represented by molecular formula 270 (16.00 g, yield 90%). 1 H NMR (400MHz, Chloroform-d) ⁇ 7.86 (s, 1H).
  • the present invention provides an organic light-emitting device based on a hole injection material composed of thiophene derivatives, furan derivatives and selenium phenol derivatives substituted by electron-deficient groups such as cyano, fluorine, pentafluorophenyl, etc., as shown in Figure 1
  • the metal cathode 191, the electron injection layer 180, the electron transport layer 160, the light emitting layer 150, the hole transport layer 140, the hole injection layer 130, the anode 120 and the glass substrate 110 are stacked in sequence from top to bottom.
  • Device preparation The process is evaporation method.
  • the metal cathode is aluminum, with a deposition rate of 0.1-0.3nm/s and a thickness of 100nm;
  • the electron injection layer uses the material synthesized by this patent and the commercial hole injection material LMZ-2178, with an evaporation rate of 0.05-0.1nm/s and a thickness of 1nm;
  • the electron transport layer uses the compound LET003 with the following structure, the evaporation rate is 0.05-0.1nm/s, and the thickness is 40nm;
  • the light-emitting layer is formed by co-doping host material and guest material.
  • the host material is the currently commercialized host material LBH001, and the guest material is LBD001 with the following structure.
  • the doping mass ratio of the host material to the guest material is 90:10.
  • the plating rate is 0.003-0.2nm/s, and the thickness is 40nm;
  • the electron blocking layer uses the compound LEB001 with the following structure, the evaporation rate is 0.05-0.1nm/s, and the thickness is 10nm;
  • the hole transport layer uses a compound NPB having the following structure, with a deposition rate of 0.05-0.1 nm/s and a thickness of 100 nm;
  • the anode 7 is made of indium tin oxide (ITO).
  • the hole injection layer materials provided by the present invention have lower turn-on voltage, higher current efficiency and longer lifespan of the device.
  • the present invention compares the HOMO and LUMO orbital energies of different materials with commercial LMZ-2178. Compare the hole injection layer material in the present invention with currently commercialized materials.
  • the hole injection layer material provided by the present invention has deeper HOMO and LUMO energy levels and a slightly higher energy band width, which is more conducive to hole injection from the anode into the organic layer. This shows that it can be better used in organic light-emitting devices to achieve better display effects.
  • the hole injection layer material provided by the present invention when applied to an organic light-emitting device, it can effectively improve the performance of the device, including efficiency and working life.
  • the structure of the perovskite solar cell provided in this embodiment is shown in FIG2 , and the specific preparation process is as follows:
  • the ITO conductive glass was washed ultrasonically with acetone, deionized water, and isopropyl alcohol in sequence, and dried under vacuum at 80°C for 12 hours.
  • a hole injection layer film is evaporated on ITO, and then PTAA is spin-coated as a hole transport layer.
  • Prepare the perovskite precursor solution dissolve it in DMSO, spin-coat it on the PTAA film, and anneal it at 100°C for 10 minutes.
  • Configure the electron transport layer solution dissolve PCBM in chlorobenzene at a concentration of 10 mg/ml, and prepare it on the perovskite film by spin coating.
  • the methanol solution of BCP was spin-coated on the PCBM, and finally the metallic silver electrode was vacuum evaporated.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

La présente invention concerne le domaine de l'émission de lumière organique, et en particulier, un matériau d'injection de trous organiques et son utilisation. Le matériau d'injection de trous organiques est un dérivé de cycle à cinq chaînons double substitué par un groupe déficient en électrons, et un cycle à cinq chaînons double comprend, mais n'est pas limité à, un cycle à cinq chaînons double composé de groupes thiophène, furane ou sélénophène. La synthèse du matériau est simple, et la production à grande échelle est facilitée. Des structures de niveau d'énergie HOMO et LUMO du matériau sont appropriées, ce qui facilite l'injection de supports. Le matériau prend un groupe substituant et le cycle à cinq chaînons double en tant que noyau, de telle sorte que la transmission de porteurs dans un dispositif est facilitée. Le matériau a un niveau d'énergie LUMO/HOMO élevé, de telle sorte que des trous peuvent être facilement transmis à partir d'une anode ITO à une couche de transport de trous. Une diode électroluminescente organique préparée à partir du matériau de couche d'injection de trous décrit est utilisée et présente une efficacité d'émission de lumière et une durée de vie de dispositif relativement élevées, peut améliorer l'efficacité de conversion photoélectrique lorsqu'elle est appliquée à une cellule solaire à pérovskite, et a une valeur commerciale relativement élevée.
PCT/CN2022/120874 2022-09-23 2022-09-23 Matériau d'injection de trous organiques et utilisation WO2024060203A1 (fr)

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