WO2021143222A1 - Matériau de transport de trous à haute performance, et procédé de préparation et application de celui-ci - Google Patents

Matériau de transport de trous à haute performance, et procédé de préparation et application de celui-ci Download PDF

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WO2021143222A1
WO2021143222A1 PCT/CN2020/120824 CN2020120824W WO2021143222A1 WO 2021143222 A1 WO2021143222 A1 WO 2021143222A1 CN 2020120824 W CN2020120824 W CN 2020120824W WO 2021143222 A1 WO2021143222 A1 WO 2021143222A1
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compound
hole transport
transport material
reaction
formula
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朱旭辉
黄小兰
彭俊彪
曹镛
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华南理工大学
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Definitions

  • the invention belongs to the technical field of organic small molecule optoelectronic materials, and relates to small organic molecule hole transport materials, in particular to a low-cost, low HOMO, high glass transition temperature hole transport material and its preparation method and application in optoelectronic devices .
  • Organic small molecule hole transport materials play an important role in the field of optoelectronic devices.
  • Organic light-emitting diodes have important application prospects in the display and lighting fields.
  • Solar cells are one of the hotspots of research, especially perovskite solar cells. The current photoelectric conversion efficiency has exceeded 23%.
  • the common organic small molecule hole transport materials in OLEDs include TPD (T g ⁇ 58°C), TAPC (T g ⁇ 79°C) and NPB (T g ⁇ 98°C), etc.
  • TPD T g ⁇ 58°C
  • TAPC T g ⁇ 79°C
  • NPB T g ⁇ 98°C
  • perovskite solar cells the commonly used hole transport materials are PTAA and spiro-OMeTAD, but the cost of the two materials is relatively high, and the price is relatively expensive. Therefore, it is necessary to further develop low-cost and high-efficiency perovskite voids. Hole transport material.
  • the purpose of the present invention is to provide a high-performance hole transport material.
  • the hole transport material has a relatively low HOMO and a high glass transition temperature. At the same time, the synthesis of the material is simple and the cost is low.
  • Another object of the present invention is to provide a method for preparing the above-mentioned low-cost, low-HOMO, and high-glass transition temperature hole transport material.
  • Another object of the present invention is to provide the application of the above-mentioned low-cost, low HOMO and high glass transition temperature hole transport material.
  • the hole transport material is used to prepare optoelectronic devices, especially OLED devices and/or solar cells.
  • a high-performance hole transport material whose structural formula is formula I:
  • Ar 1 and Ar 2 are independently unsubstituted or substituted carbazole units, fluorene units, dibenzopyran units, and dibenzothiophene units; the substituted substituents are each having 1 to 6 carbon atoms. ⁇ alkyl, alkoxy or alkylthio;
  • the Ar 1 and Ar 2 groups alone are preferably one of the following chemical structures:
  • the attachment site in Represents the attachment site on the Ar 1 or Ar 2 group, the attachment site includes at least -1-, -2-, -3-, -4-, -5-, -6-, -7-,- One of 8-bits.
  • the high-performance hole transport material (compound of formula I) is preferably one or more of the following structures:
  • the preparation method of the high-performance hole transport material includes the following steps:
  • Ar represents one of Ar 1 or Ar 2 ;
  • Ar represents one of Ar 1 or Ar 2 ;
  • the catalyst in step (1) is preferably methanesulfonic acid or p-toluenesulfonic acid;
  • the protective atmosphere in step (1) is preferably nitrogen atmosphere or argon atmosphere;
  • the organic solvent in step (1) is preferably ortho Xylene, meta-xylene or p-xylene;
  • the heating temperature of the reaction in step (1) is 150-210°C; the reaction time is 3-15h.
  • step (1) the molar ratio of the catalyst, 6-bromo-2-naphthol and aniline is (0.15-0.5):1:(1.5-5), preferably 0.2:1:3.
  • the purification treatment in step (1) refers to cooling the system to 40-80°C after the reaction, adding potassium acetate or sodium acetate and ethanol for stirring, then distilling under reduced pressure to remove the liquid solvent, adding warm water, stirring, suction filtering, and taking filtration The cake is washed and refluxed with ethanol, cooled and filtered with suction to obtain a solid product, which is dried.
  • the organic solvent in step (2) is one or more of anhydrous tetrahydrofuran, anhydrous DMF and anhydrous toluene;
  • the catalytic system in step (2) includes a catalyst, and the catalyst is CuI/trans 1,2-ring A combination of hexamethylene diamine and CuI/1,10-phenanthroline (the molar ratio of CuI to trans 1,2-cyclohexanediamine is preferably 1:5, and the ratio of CuI to 1,10-phenanthroline The molar ratio is preferably 1:2);
  • the catalytic system in step (2) includes a basic compound, and the basic compound is one or more of sodium tert-butoxide, potassium tert-butoxide, potassium hydroxide and sodium hydroxide
  • the reaction in step (2) is a heating-reflux reaction, and the heating-reflux reaction is a reaction at 70-130°C for 8-20h;
  • step (2) the molar ratio of the catalyst, the basic compound, the iodine-substituted compound of Ar or the bromine-substituted compound of Ar to the compound of formula II is (0.005 ⁇ 0.4): (2 ⁇ 6): (1.1 ⁇ 2):1, Preferably, it is (0.01 to 0.3): (3 to 4): (1.2 to 1.4):1.
  • the protective atmosphere in step (3) is a nitrogen atmosphere or an argon atmosphere;
  • the organic solvent in step (3) is one or more of anhydrous tetrahydrofuran or anhydrous DMF;
  • the catalytic system in step (3) includes a catalyst,
  • the catalyst is Pd(PPh 3 ) 2 Cl 2 ;
  • the catalytic system in step (3) includes a basic compound, and the basic compound is one or more of potassium acetate or sodium acetate; the reaction in step (3) React at 80 ⁇ 130°C for 7 ⁇ 15h;
  • Step (3) The molar ratio of the compound of formula III, dual pinacol borate, catalyst and basic compound is 1:(1.1 ⁇ 1.5):(0.01 ⁇ 0.03):(2 ⁇ 4), preferably 1:1.2:0.01:3.
  • step (3) means to evaporate the reaction suspension under reduced pressure to remove the reaction solvent, then add dichloromethane and water for extraction, after separation, the organic layer is dried and concentrated under reduced pressure to remove the organic solvent, and then The column chromatography is separated and concentrated to obtain a solid product.
  • the developing solvent of the column chromatography is petroleum ether and dichloromethane, and the volume ratio is (4:1) to (1:1).
  • the protective atmosphere in step (4) is one of nitrogen or argon atmosphere;
  • the organic solvent in step (4) is one or more of tetrahydrofuran or toluene;
  • the catalytic system in step (4) includes a catalyst and a phase A transfer agent, the catalyst is tetrakistriphenylphosphine palladium, and the phase transfer agent is ethanol;
  • the catalytic system in step (4) includes a basic compound, and the basic compound is added in the form of an aqueous solution.
  • the concentration of the aqueous solution is 2mol/L; the reaction in step (4) refers to the reaction at 80-130°C for 5-15 hours; the molar ratio of the compound of formula III and the compound of formula IV in step (4) is (1 ⁇ 1.5 ):1; the molar ratio of the tetrakistriphenylphosphine palladium, the basic compound and the compound of formula IV is (0.01 ⁇ 0.03):(2 ⁇ 6):1.
  • step (4) includes extraction, column chromatography separation, heating and reflux washing and suction filtration; the extraction refers to the crude product after the reaction is subjected to reduced pressure rotary evaporation to remove the reaction solvent, and then dichloromethane and The water was fully stirred and then separated. The organic layer was dried over magnesium sulfate and then rotary evaporated to remove organic solvents such as dichloromethane to obtain a crude solid product; the developing solvent for column chromatography was a mixture of petroleum ether and dichloromethane.
  • the mixed solvent has a volume ratio of (5:1) to (2:1); the detergent used for heating and reflux washing is ethanol.
  • the application of the high-performance hole transport material in optoelectronic devices especially the application in low-working voltage, long-life OLED devices and high-performance solar cells.
  • the invention adopts an electron-rich aromatic amine structure, so that this type of organic small molecule materials have good hole transport characteristics, and thus are used as hole transport materials in optoelectronic devices; at the same time, they have a certain rigidity and good hole mobility.
  • the end group substitution unit (such as fluorene unit, carbazole unit, dibenzofuran unit, dibenzothiophene unit, etc.), due to the enhancement of rigidity, makes the glass transition temperature of this type of organic small molecule materials increase, which is beneficial to increase
  • fluorene units and other substituted end groups can also effectively adjust the HOMO energy level of the compound, making the HOMO energy level of the compound deeper, thereby reducing the operating voltage of the OLED device, improving the efficiency of the OLED device, and improving the performance of the solar cell;
  • the binaphthyl group used in the bridge also effectively enhances the rigidity of the compound, which helps to further increase the glass transition temperature of the material, thereby improving the thermal stability of the material and
  • the present invention has the following advantages and beneficial effects:
  • the hole transport material of the present invention uses a binaphthyl group as a bridge group and a fluorene group as an end group to greatly enhance the rigidity of the compound, thereby effectively increasing the glass transition temperature of the material, and making the film morphology stable Enhanced performance, which can meet the requirements of the glass transition temperature of the materials for the industrial application of OLEDs;
  • the fluorene group and other end groups introduced by the hole transport material of the present invention can reduce the HOMO energy level of the compound to a certain extent, which is beneficial to improve the performance of the optoelectronic device;
  • the hole transport material of the present invention has good hole transport performance and a suitably low HOMO energy level. It is expected to reduce the working voltage of the device and increase the life of the device when applied to OLED devices, and it is beneficial to improve the performance of the device when applied to solar cells. .
  • the hole transport material of the present invention is simple to synthesize, has low cost, and is beneficial to large-scale production.
  • Figure 1 is a hydrogen nuclear magnetic resonance spectrum of the hole transport material A-1 with high glass transition temperature prepared in Example 1;
  • Example 2 is a carbon nuclear magnetic resonance spectrum of the hole transport material A-1 with high glass transition temperature prepared in Example 1;
  • Example 3 is the ultraviolet-visible absorption and fluorescence emission spectra of the high glass transition temperature hole transport material A-1 prepared in Example 1;
  • Example 4 is a DSC curve of the hole transport material A-1 with high glass transition temperature prepared in Example 1;
  • Example 5 is a low kinetic energy region (a) and a valence band spectrum near the Fermi level region (b) of the ultraviolet photoelectron energy spectrum of the hole transport material A-1 with high glass transition temperature prepared in Example 1;
  • Figure 6 is the current density-voltage-luminance curve (a) of the organic electroluminescent red phosphorescent device comparing the hole transport material A-1 with high glass transition temperature prepared in Example 1 and the common hole transport material NPB (a); current efficiency -Brightness-power efficiency curve (b); external quantum efficiency-brightness curve (c); electroluminescence intensity-wavelength curve (d); brightness-time curve (e) graph and voltage-time curve (f);
  • Example 7 is a hydrogen nuclear magnetic resonance spectrum of the hole transport material A-2 with high glass transition temperature prepared in Example 2;
  • Figure 9 is a DSC curve of the high glass transition temperature hole transport material A-2 prepared in Example 2;
  • Figure 11 is the current density-voltage-luminance curve (a) of the organic electroluminescent red phosphorescent device comparing the hole transport material A-2 with high glass transition temperature prepared in Example 2 and the common hole transport material NPB (a); current efficiency -Brightness-power efficiency curve (b); external quantum efficiency-brightness curve (c); electroluminescence intensity-wavelength curve (d); brightness-time curve (e) graph and voltage-time curve (f).
  • the method for preparing the hole transport material A-1 with high glass transition temperature of this embodiment includes the following steps:
  • the developing solvent of column chromatography is a mixed solvent of petroleum ether: dichloromethane with a volume ratio of 4:1.
  • the separated solid product was washed with ethanol under reflux, filtered with suction, and dried to obtain a pure solid product with a yield of about 86% (2.9 g).
  • FIG. 1 is a hydrogen nuclear magnetic resonance spectrum of the hole transport material A-1 with a high glass transition temperature prepared in Example 1 of the present invention.
  • Figure 2 is a carbon nuclear magnetic resonance spectrum of the hole transport material A-1 with a high glass transition temperature prepared in Example 1 of the present invention.
  • the optical band gap is calculated to be 2.82 eV based on the position of the absorption edge of the film.
  • DSC Differential scanning calorimetry
  • NETZSCH DSC 204 F1 thermal analyzer Under the protection of nitrogen, the temperature rises from -30°C to 300°C at a rate of 10°C/min, and then decreases to -30°C at 20°C/min. °C, keep the temperature for 5 min, and test again at a temperature increase rate of 10°C/min to 300°C.
  • Example 4 is a differential scanning calorimetry curve of the hole transport material with high glass transition temperature prepared in Example 1 of the present invention.
  • the differential scanning calorimetry curve (DSC curve) of Figure 4 shows that the glass transition temperature of the material is relatively high, about 146°C. It can be seen that A-1 has good thermal stability and morphological stability.
  • the HOMO energy level was calculated by ultraviolet photoelectron spectroscopy, and the A-1 thin film prepared in Example 1 was vapor-deposited with a thickness of 10 nm on ITO. 5 shows the low kinetic energy region (a) and the valence band spectrum near the Fermi level (b) of the ultraviolet photoelectron energy spectrum of the hole transport material with high glass transition temperature prepared in Example 1.
  • the calculated HOMO energy level is -5.39eV, which shows that the suitable HOMO value of the material is beneficial to the transport of holes and improves the device performance.
  • the LUMO energy level is about -2.57eV.
  • A-1 is used as the doped hole transport material, and compared with the common hole transport material NPB, the characterization results of the organic electro-red phosphorescent device using the vacuum evaporation method:
  • HT21:H09 is the hole injection layer
  • HT18 is the exciton blocking layer
  • PH315:RD314 is the red phosphorescent light-emitting layer
  • TRZ-m-Phen is the electron transport layer
  • E02 is the electron injection layer
  • HT21, H09, HT18, PH315, RD314 and E02 are all commercial code materials
  • HT21, H09, HT18, PH315 are purchased from Changzhou Qiangli Yulei Optoelectronics Materials Co., Ltd.
  • RD314 and E02 were purchased from Jilin Aolaide Optoelectronic Materials Co., Ltd.).
  • Figure 6 (a) is the high glass transition temperature hole transport material A-1 prepared in Example 1. Compared with the common hole transport material NPB, the current density-voltage-brightness curve of the organic electroluminescent red phosphorescent device ;
  • Figure 6 (b) is the high glass transition temperature hole transport material A-1 prepared in Example 1. Compared with the common hole transport material NPB, the current efficiency-brightness-power efficiency of the organic electroluminescence phosphorescent device curve;
  • Figure 6 (c) is the high glass transition temperature hole transport material A-1 prepared in Example 1. Compared with the common hole transport material NPB, the external quantum efficiency-brightness curve of the organic electroluminescence red phosphorescent device; The coordinate value "1E+02" in the figure represents e 2 ;
  • Figure 6 (d) is the high glass transition temperature hole transport material A-1 prepared in Example 1. Compared with the common hole transport material NPB, the electroluminescence intensity-wavelength curve of the organic electroluminescence red phosphorescent device ;
  • Figure 6 (e) is the high glass transition temperature hole transport material A-1 prepared in Example 1. Compared with the common hole transport material NPB, the brightness-time curve of the organic electroluminescent red phosphorescent device is shown in the figure; The coordinate value "E3" represents e 3 ;
  • Figure 6 (f) is the high glass transition temperature hole transport material A-1 prepared in Example 1, compared with the common hole transport material NPB, in the voltage-time curve of the organic electroluminescence red phosphorescent device;
  • the initial brightness of the device based on A-1 is higher than that based on NPB when the current density is 50mA cm -2 .
  • its lifetime is t 95 (t 95 is the device The time it takes for the brightness to decay from the initial brightness to 95% of its initial brightness) is 17.4h.
  • the t 95 under the initial brightness of 1000cd m -2 is as high as 4724h, and the NPB-based device is converted to be at 1000cd
  • the t 95 under the initial brightness of m -2 is only 3763 h, indicating that A-1 has very good device stability in the thermally evaporated red phosphorescent device, and the stability is significantly better than that of NPB.
  • Step (1) is exactly the same as step (1) in embodiment 1, and will not be repeated;
  • Step 2 Preparation of N-(6-bromonaphthalen-2-yl)-9-methyl-N-phenyl-9H-carbazole-3-amine (5), reaction equation:
  • step (2) The difference between the operation process of step (2) and the step (2) of Example 1 is that one of the reactants of step (2) in Example 1 is 2-iodo-9,9-dimethyl-9H-fluorene with 3 -Iodine-9-methyl-9H-carbazole is used instead.
  • Petroleum ether is used as the developing solvent for column chromatography. After the unreacted 3-iodo-9-methyl-9H-carbazole is removed, the developing solvent Changed to a mixed solvent of petroleum ether and dichloromethane, the volume ratio is about 4:1; the yield is about 90% (10.1g);
  • Step 3 9-Methyl-N-phenyl-N-(6-(4,4,5,5-tetramethyl-1,3,2-dioxaboroborin-2-yl)naphthalene-
  • 2-yl)-9H-carbazole-3-amine (6) the reaction equation:
  • step (3) is different from step (3) in Example 1 in that one of the reactants in step (3) in Example 1, compound 3 is replaced with compound 5, and the yield is 93% (8.37g);
  • Step 4 N',N"-bis(9,9-dimethyl-9H-carbazol-3-yl)-N',N"-diphenyl-[2,2'-binaphthyl]-6
  • 6'-diamine (A-2) N',N"-bis(9,9-dimethyl-9H-carbazol-3-yl)-N',N"-diphenyl-[2,2'-binaphthyl]-6
  • step (4) is different from step (4) in Example 1 in that the reactant compound 3 of step (3) in Example 1 is replaced by compound 5, and compound 4 is replaced by compound 6, and the yield is 88%. (7g).
  • FIG. 7 is a hydrogen nuclear magnetic resonance spectrum of the hole transport material A-2 with a high glass transition temperature prepared in Example 2 of the present invention.
  • the optical band gap is calculated to be 2.73 eV based on the position of the absorption edge of the film.
  • DSC Differential scanning calorimetry
  • NETZSCHDSC 204 F1 thermal analyzer Under the protection of nitrogen, the temperature rises from -30°C to 400°C at a rate of 10°C/min, and then decreases to -30°C at 20°C/min. , Constant temperature for 5 minutes, and test again with a temperature rise rate of 10°C/min to 400°C.
  • Figure 9 is a differential scanning calorimetry (DSC) curve of the high glass transition temperature hole transport material A-2 prepared in Example 2 of the present invention. It can be seen from Figure 9 that the glass transition temperature of A-2 is relatively high, about 161°C. It can be seen that A-2 has good thermal stability and morphological stability.
  • DSC differential scanning calorimetry
  • the HOMO energy level was calculated by UV photoelectron spectroscopy, and A-2 film of 10nm was deposited on ITO. 10 shows the low kinetic energy region (a) and the valence band spectrum near the Fermi level (b) of the ultraviolet photoelectron energy spectrum of the hole transport material with high glass transition temperature prepared in Example 2.
  • the HOMO energy level is calculated to be -5.33 eV; the LUMO energy level is calculated to be about -2.60 eV according to the optical band gap of A-2.
  • A-2 is used as the doped hole transport material, and compared with the common hole transport material NPB, the characterization results of the organic electro-red phosphorescent device using the vacuum evaporation method:
  • HT21:H09 is the hole injection layer
  • HT18 is the exciton blocking layer
  • PH315:RD314 is the red phosphorescent light-emitting layer
  • TRZ-m-Phen is the electron transport layer (preparation method Refer to the Chinese Patent Publication CN 108409730 A)
  • E02 is the electron injection layer
  • HT21, H09, HT18, PH315, RD314 and E02 are all commercial code materials.
  • Figure 11 (a) is the high glass transition temperature hole transport material A-2 prepared in Example 2. Compared with the common hole transport material NPB, the current density-voltage-brightness curve of the organic electroluminescent red phosphorescent device ;
  • Figure 11 (b) shows the high glass transition temperature hole transport material A-2 prepared in Example 2. Compared with the common hole transport material NPB, the current efficiency-brightness-power efficiency of the organic electroluminescence phosphorescent device curve;
  • (C) in Figure 11 is the high glass transition temperature hole transport material A-2 prepared in Example 2. Compared with the common hole transport material NPB, the external quantum efficiency-brightness curve of the organic electro-red phosphorescent device;
  • Figure 11 (d) is the high glass transition temperature hole transport material A-2 prepared in Example 2. Compared with the common hole transport material NPB, the electroluminescence intensity-wavelength curve of the organic electroluminescence red phosphorescent device ;
  • (F) in FIG. 11 is the voltage-time curve of the high glass transition temperature hole transport material A-2 prepared in Example 2, compared with the common hole transport material NPB, in the organic electroluminescence red phosphorescent device.
  • the high glass transition temperature hole transport material of the present invention is used to prepare an OLED device (used as a hole transport layer).
  • the device structure includes ITO, a hole injection/transport layer, a light emitting layer, and an electron injection/ Transmission layer, metal electrode;
  • the high glass transition temperature hole transport material of the present invention is used to prepare the front-mounted device (for the hole transport layer) of solar cells (organic solar cells or perovskite solar cells), and the device structure includes ITO from bottom to top. /FTO, hole transport layer, active layer, cathode interface layer, metal electrode;
  • the high glass transition temperature hole transport material of the present invention is used to prepare flip-chip devices (for hole transport layers) of solar cells (organic solar cells or perovskite solar cells), and the device structure includes from bottom to top. ITO/FTO, cathode interface layer, active layer, hole transport layer, metal electrode.

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  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Electromagnetism (AREA)
  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne un matériau de transport de trous à haute performance, et un procédé de préparation de celui-ci et une application de celui-ci. La structure du matériau de transport de trous est représentée par la formule (I), dans laquelle Ar1 et Ar2 sont indépendamment un motif carbazole non substitué ou substitué, un motif fluorène, un motif dibenzofurane et un motif dibenzothiophène ; et un substituant substitué est alkyle, alcoxy ou alkylthio ayant de 1 à 6 atomes de carbone. Le matériau de transport de trous présente une température de transition vitreuse élevée, un faible niveau d'énergie HOMO et une bonne mobilité de trous. Le procédé de préparation du matériau de transport de trous est simple, la purification de produit est facile et le coût est faible, et celui-ci est utilisé pour préparer un dispositif photoélectrique, en particulier un dispositif OLED et un dispositif de cellule solaire.
PCT/CN2020/120824 2020-01-17 2020-10-14 Matériau de transport de trous à haute performance, et procédé de préparation et application de celui-ci WO2021143222A1 (fr)

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