WO2023000280A1 - Blue-light perovskite light-emitting diode based on modified hole transport layer and preparation method therefor - Google Patents

Blue-light perovskite light-emitting diode based on modified hole transport layer and preparation method therefor Download PDF

Info

Publication number
WO2023000280A1
WO2023000280A1 PCT/CN2021/108008 CN2021108008W WO2023000280A1 WO 2023000280 A1 WO2023000280 A1 WO 2023000280A1 CN 2021108008 W CN2021108008 W CN 2021108008W WO 2023000280 A1 WO2023000280 A1 WO 2023000280A1
Authority
WO
WIPO (PCT)
Prior art keywords
transport layer
light
hole transport
blue
perovskite
Prior art date
Application number
PCT/CN2021/108008
Other languages
French (fr)
Chinese (zh)
Inventor
唐建新
王经坤
李艳青
Original Assignee
苏州大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 苏州大学 filed Critical 苏州大学
Priority to PCT/CN2021/108008 priority Critical patent/WO2023000280A1/en
Publication of WO2023000280A1 publication Critical patent/WO2023000280A1/en

Links

Classifications

    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to the field of preparation of perovskite photoelectric devices, in particular to a method for preparing a blue perovskite light-emitting diode based on interface modification of a hole transport layer.
  • Metal halide perovskite (Perovskite) is a popular material in international research after graphene. It has excellent photoelectric properties, low cost and solution processing, and has been widely studied in the field of optoelectronic device technology; among them, perovskite solar cells Commercial large-scale preparation has been realized, and perovskite light-emitting diodes have also achieved rapid development in the past 10 years, and have good application prospects in the fields of display and lighting.
  • perovskite light-emitting diodes are high color purity and solution processing.
  • the external quantum efficiency of green and red perovskite light-emitting diodes has exceeded 20%, and the device life has been increased to hundreds of hours; however, the device performance of blue perovskite light-emitting diodes is still very poor, which limits the performance of perovskite light-emitting diodes.
  • the common way to prepare blue-light perovskite is to introduce a certain amount of chloride ions into the perovskite of the bromine system to adjust the luminescence spectrum, but the introduction of chloride ions will make the uniformity and crystallinity of the perovskite film worse, greatly reducing the Luminescent performance of the device.
  • the anti-solvent method is often used to improve the crystallization quality of perovskite films, but this method increases the complexity of the operation, and is difficult to apply to the large-area device preparation process of the industrial solution method, such as printing and inkjet printing; in The introduction of micro-nano structures into the device to enhance optical coupling can improve the light output of the device, but the processing technology is complicated and the manufacturing cost is increased; the composition adjustment of the perovskite layer is more advantageous than the previous two methods, but the actual operation is also relatively Complicated, it is easy to cause a large shift in the emission wavelength of perovskite.
  • the object of the present invention is to provide a blue-light perovskite light-emitting diode based on a modified hole transport layer and a preparation method thereof, which are suitable for many applications such as spin coating, scraping coating, printing and inkjet printing in solution processing.
  • a current preparation technology is to provide a blue-light perovskite light-emitting diode based on a modified hole transport layer and a preparation method thereof, which are suitable for many applications such as spin coating, scraping coating, printing and inkjet printing in solution processing.
  • the technical scheme adopted in the present invention is: a blue-light perovskite light-emitting diode based on a modified hole transport layer, the hole transport layer of which is an alcohol amine modified hole transport layer. Further, the blue perovskite light-emitting diode based on the modified hole transport layer also includes a blue perovskite light-emitting layer, an electron transport layer, an anode and a cathode, all of which are conventional techniques obtained according to existing materials and preparation methods.
  • the inventiveness of the present invention lies in modifying the hole transport layer with alcohol amine as the hole transport layer in the perovskite light-emitting device, other structures or compositions are all prior art, and the alcohol amine is preferably propanolamine (Propanolamine).
  • the volume of the alcohol amine is 1-3 ⁇ of the volume of the stock solution of the hole transport layer.
  • the alcohol amine and the stock solution of the hole transport layer are mixed at a volume ratio of 1-3:1000 and stirred evenly to obtain a modified hole transport layer solution, wherein the doping concentration of the alcohol amine is 1-3 ⁇ l/ml.
  • the modified hole transport layer solution is prepared into a film according to a conventional method, and used as a hole transport layer in a perovskite light-emitting device.
  • the thickness of the alcohol amine-modified hole transport layer is 30-40 nm, and the thickness of the blue-light perovskite light-emitting layer is 20-25 nm. nm, the thickness of the electron transport layer is 40 ⁇ 50 nm, the thickness of LiF is 1 nm, and the thickness of Al is 90 ⁇ 120 nm.
  • the invention discloses a preparation method of the above-mentioned blue light perovskite light-emitting diode based on a modified hole transport layer, which includes the following steps: adding alcohol amine into the stock solution of the hole transport layer to obtain a modified hole transport layer solution, and then adding the modified The hole transport layer solution is spin-coated on the surface of the anode, annealed to obtain the hole transport layer, and then the blue perovskite light-emitting layer, electron transport layer and cathode are prepared to obtain the blue perovskite light-emitting diode based on the modified hole transport layer.
  • the stock solution of the hole transport layer, the blue light perovskite light-emitting layer, the electron transport layer, the anode and the cathode disclosed in the present invention are all prior art.
  • the stock solution of the hole transport layer is a PEDOT:PSS stock solution, and the blue light perovskite emits light.
  • the raw materials for the preparation of the layer include CsBr, PbBr 2 , PbCl 2 , KBr, p-fluorophenethylamine bromide (pf-PEABr), and formamidine hydrobromide (FABr).
  • the composition of the blue perovskite light-emitting layer is 1.4:1:0.25:0.4:0.15 ⁇ 0.16,
  • the molar ratio of PbBr 2 and PbCl 2 is 2 ⁇ 2.2:1;
  • the electron transport layer is TPBi, and ITO and LiF/Al are respectively set as the anode and cathode of the perovskite light-emitting diode.
  • the preparation methods of the blue light perovskite light-emitting layer, the electron transport layer, the anode and the cathode also belong to the prior art.
  • the present invention has the following advantages and beneficial effects: (1)
  • the modified material of the present invention is low in cost, the method for modifying the hole transport layer is simple to operate, and the device structure and preparation process are not affected before and after modification.
  • the hole transport layer modified by the present invention has propanolamine molecules on the surface, which can improve the uniformity of film formation of the blue light perovskite film, is compatible with scraping, printing and inkjet printing technology, and is suitable for industrial preparation Large-area perovskite light-emitting devices.
  • the modified material propanolamine of the present invention can regulate perovskite crystallization, effectively passivate perovskite defects, stabilize the perovskite structure, and enhance the luminescent properties and stability of perovskite thin films.
  • the brightness and external quantum efficiency of the prepared blue perovskite light-emitting diodes have been effectively improved, and the working life has reached the advanced level of research in related fields.
  • Fig. 1 is a cross-sectional scanning electron microscope test result of a blue perovskite light-emitting diode based on a modified hole transport layer prepared in the present invention.
  • Fig. 2 is the test result of the contact angle of the PEDOT:PSS layer in Example 1 and Comparative Example 1 of the present invention.
  • Fig. 3 is the test results of the steady-state photoluminescence spectrum of the blue-light perovskite light-emitting layer in Example 1 and Comparative Example 1 of the present invention.
  • FIG. 4 shows the test results of the transient fluorescence lifetime of the blue-light perovskite light-emitting layer in Example 1 and Comparative Example 1 of the present invention.
  • Example 5 is the X-ray diffraction spectrum of the blue-light perovskite light-emitting layer in Example 1 and Comparative Example 1 of the present invention.
  • FIG. 6 is the electroluminescence spectrum diagram of the blue perovskite light-emitting diodes prepared in Example 1 and Comparative Example 1 of the present invention.
  • Example 7 is a voltage-current density curve and a voltage-brightness curve of the blue perovskite light-emitting diodes prepared in Example 1 and Comparative Example 1 of the present invention.
  • FIG. 8 is the current density-external quantum efficiency curves of the blue perovskite light-emitting diodes prepared in Example 1 and Comparative Example 1 of the present invention.
  • Fig. 9 is a curve of decay with time at an initial luminance of 100 cd/m 2 of the blue perovskite light-emitting diodes prepared in Example 1 and Comparative Example 1 of the present invention.
  • FIG. 10 is a working photo of the large-area (100 mm 2 ) blue perovskite light-emitting diode prepared in Example 2 of the present invention.
  • Fig. 11 is the voltage-current density curve and voltage-brightness curve of the large-area (100 mm 2 ) blue perovskite light-emitting diode prepared in Example 2 of the present invention.
  • Fig. 12 is the current density-external quantum efficiency curve of the large-area (100 mm 2 ) blue perovskite light-emitting diode prepared in Example 2 of the present invention.
  • the present invention will be further explained and illustrated below in conjunction with specific embodiments. It should be understood that the following examples are used to illustrate the present invention, but not to limit the scope of the present invention. The invention is capable of other embodiments and of being practiced or of being carried out in various ways.
  • the specific preparation method and testing method of the present invention are conventional methods in this field; the raw materials adopted are all existing products, which meet the conventional requirements of perovskite light-emitting diodes, such as PEDOT:PSS stock solution is widely used Al 4083, the solvent is water, solid The content is 1.5wt.%, the mass ratio of PEDOT and PSS is 1:6; the chemical structural formula of propanolamine is as follows: .
  • the preparation method of the present invention based on the blue light perovskite light-emitting diode of the modified hole transport layer is the following detailed steps: S1. Ultrasonic cleaning of the anode substrate with diluted Decon aqueous solution, followed by Rinse the ITO anode substrate with deionized water, then ultrasonically clean it in ethanol and isopropanol for 5-10 minutes, and finally dry it in an oven.
  • the PEDOT:PSS solution was spin-coated at 4000 rpm/min for 40 s, and then annealed at 140°C for 15 minutes at a high temperature to form a hole transport layer.
  • the inventiveness of the present invention does not lie in the selection of specific raw materials for the preparation of perovskite light-emitting diodes and the limitation of the preparation parameters, but in the first use of alcohol amines, especially propanolamines, as modifiers doped into the hole transport layer, thereby effectively improving the hole transport layer based on the modification.
  • the performance of the device at the transport layer does not lie in the selection of specific raw materials for the preparation of perovskite light-emitting diodes and the limitation of the preparation parameters, but in the first use of alcohol amines, especially propanolamines, as modifiers doped into the hole transport layer, thereby effectively improving the hole transport layer based on the modification.
  • the performance of the device at the transport layer does not lie in the selection of specific raw materials for the preparation of perovskitemitting diodes and the limitation of the preparation parameters, but in the first use of alcohol amines, especially propanolamines, as modifiers doped into the hole transport layer, thereby effectively improving the
  • Example 1 A blue-light perovskite light-emitting diode based on a modified hole transport layer.
  • the preparation method is as follows: (1) ultrasonically clean the ITO anode substrate with a 20-fold diluted Decon aqueous solution for 5 minutes, and then deionize the ITO with deionized water. The anode substrate was rinsed clean, then placed in ethanol and isopropanol for ultrasonic cleaning for 5 minutes, and finally dried in an oven.
  • Comparative example 1 other steps of this comparative example are completely consistent with embodiment 1, difference is: PEDOT:PSS stoste solution does not need doping treatment.
  • PEDOT:PSS stoste solution does not need doping treatment.
  • the PEDOT:PSS stock solution was spin-coated on the surface of the ITO anode at 4000 rpm/min for 40 s, and then annealed at 140 °C for 15 minutes to form a hole transport layer.
  • Performance test results The cross-sectional scanning electron microscope image of the blue perovskite light-emitting diode based on the modified hole transport layer prepared in Example 1 is shown in Figure 1.
  • the thicknesses of the hole transport layer and the blue perovskite light-emitting layer are respectively 34nm , 24 nm, other embodiments and comparative examples are consistent.
  • the contact angle test was measured by a contact angle tester (DataPhysics Instruments GmbH); the steady-state photoluminescence spectrum was measured by a FluoroMax-4 fluorescence spectrometer (Horiba Jobin Yvon); the transient fluorescence lifetime test was Using a Quantaurus-Tau fluorescence lifetime spectrometer (C11367-32, Hamamatsu Photonics); the X-ray diffraction spectrum of the perovskite film was obtained using a diffractometer (D8 Discover) planar mode recording; blue light perovskite light-emitting diode device performance test is using a computer-controlled programmable power supply (Keithley 2400) and a photometer/spectrometer (PhotoResearch PR655) Simultaneously measure the current density-voltage-luminance (J-V-L) characteristics and electroluminescence spectrum of the device, the test system is based on the measured The J-V-L characteristics and the electroluminescence spectrum with Lambertian distribution automatically
  • the contact angle of the PEDOT:PSS layer modified by propanolamine in Example 1 is significantly smaller than that of the unmodified PEDOT:PSS layer in Comparative Example 1, indicating that the hole transport layer disclosed by the present invention has good hydrophilicity sex.
  • the photoluminescence intensity of the blue perovskite light-emitting layer is about doubled, and the carrier lifetime is also greatly increased, indicating that propanolamine modification can passivate the perovskite layer , to suppress nonradiative recombination.
  • the numbers in parentheses in the figure indicate crystal planes, and after propanolamine modification, the crystallinity of the blue perovskite light-emitting layer is enhanced.
  • the turn-on voltage of the device dropped from 4 V to 3.4 V, indicating that the carrier injection balance in the device was improved; the blue perovskite based on the modified hole transport layer prepared in this example 1 emits light
  • the diode emits at a wavelength of 479 nm, the highest brightness is 620 cd/m 2 , the highest external quantum efficiency is 6.6%, and the T 50 working life (the time it takes for the brightness to drop to half) at an initial brightness of 100 cd/m 2 is as long as 420 s.
  • Embodiment 2 The difference between this embodiment and Embodiment 1 is that in step (1), the effective area of the ITO anode substrate used is different, and the size of the light emitting area of the final device is different.
  • the light emitting area of the blue perovskite light emitting diode based on the modified hole transport layer is 100 mm 2 .
  • the rest of the parameters are the same. As follows: (1) Ultrasonic clean the ITO anode substrate with a 20-fold diluted Decon aqueous solution for 5 minutes, then rinse the ITO anode substrate with deionized water, then place it in ethanol and isopropanol for 5 minutes, and finally place it in an oven drying.
  • the working photo of the device in this embodiment is shown in FIG. 10 , and the light emitting area is a square of 1 cm*1 cm.
  • the performance parameters of the device in this embodiment are shown in Figure 11 and Figure 12, the highest brightness of the device is 627 cd/m 2 , and the highest external quantum efficiency is 5.1%.
  • Comparative Example 2 A blue-light perovskite light-emitting diode based on a modified hole transport layer.
  • the preparation method is as follows: (1) ultrasonically clean the ITO anode substrate with 20 times diluted Decon aqueous solution for 5 minutes, and then deionize the ITO with deionized water. The anode substrate was rinsed clean, then placed in ethanol and isopropanol for ultrasonic cleaning for 5 minutes, and finally dried in an oven.
  • the highest brightness of the device is 268 cd/m 2 , the highest external quantum efficiency is 3.6%, and the emission wavelength is 479 nm.
  • Example 3 A blue-light perovskite light-emitting diode based on a modified hole transport layer.
  • the preparation method is as follows: (1) ultrasonically clean the ITO anode substrate with a 20-fold diluted Decon aqueous solution for 5 minutes, and then deionize the ITO with deionized water. The anode substrate was rinsed clean, then placed in ethanol and isopropanol for ultrasonic cleaning for 5 minutes, and finally dried in an oven.
  • the highest brightness of the device is 473 cd/m 2 , the highest external quantum efficiency is 4.9%, and the emission wavelength is 481nm.
  • Example 4 A blue-light perovskite light-emitting diode based on a modified PEDOT:PSS layer.
  • the preparation method is as follows: (1) Ultrasonic cleaning of the ITO anode substrate with 20-fold diluted Decon aqueous solution for 5 minutes, and then deionized water The ITO anode substrate was rinsed clean, then placed in ethanol and isopropanol for ultrasonic cleaning for 5 minutes, and finally dried in an oven.
  • the highest brightness of the device is 383 cd/m 2 , the highest external quantum efficiency is 4.3%, and the emission wavelength is 476 nm.
  • Example 5 A blue-light perovskite light-emitting diode based on a modified PEDOT:PSS layer.
  • the preparation method is as follows: (1) Ultrasonic cleaning of the ITO anode substrate with 20-fold diluted Decon aqueous solution for 5 minutes, and then deionized water The ITO anode substrate was rinsed clean, then placed in ethanol and isopropanol for ultrasonic cleaning for 5 minutes, and finally dried in an oven.
  • the highest brightness of the device is 256 cd/m 2 , the highest external quantum efficiency is 4.0%, and the emission wavelength is 473 nm.
  • each layer structure above can also choose known methods such as solution method scraping coating, printing, inkjet printing; those skilled in the art can easily understand that the above is only a specific example of the present invention.
  • the embodiment is only used to limit the protection scope of the present invention, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Abstract

The present invention relates to a blue-light perovskite light-emitting diode based on a modified hole transport layer and a preparation method therefor, a device comprising an anode substrate, a modified hole transport layer, a perovskite light-emitting layer, an electron transport layer, and a cathode. In the present invention, a propanolamine molecular additive is creatively introduced, so that crystal growth of a blue-light perovskite light-emitting layer can be effectively controlled, causing it to form high-quality light-emitting film with high uniformity, high crystallinity and low defect density, photoluminescence characteristics and spectral stability of a thin film are increased, and brightness, external quantum efficiency and working life of the prepared blue-light perovskite light-emitting diode are obviously improved. The modification method of the present invention is low-cost, is simple to operate, has significant effects, and is applicable to various current preparation processes, such as spin coating, blade coating, printing, and inkjet printing.

Description

基于修饰空穴传输层的蓝光钙钛矿发光二极管及其制备方法Blue-light perovskite light-emitting diode based on modified hole transport layer and its preparation method 技术领域technical field
本发明涉及钙钛矿光电器件制备领域，具体涉及一种基于空穴传输层界面修饰的蓝光钙钛矿发光二极管制备方法。The invention relates to the field of preparation of perovskite photoelectric devices, in particular to a method for preparing a blue perovskite light-emitting diode based on interface modification of a hole transport layer.
背景技术Background technique
金属卤化物钙钛矿（Perovskite）是继石墨烯之后国际研究的热门材料，其具有优良的光电性质，成本低廉而且可溶液加工，在光电器件技术领域被广泛研究；其中，钙钛矿太阳能电池已经实现商业化大规模制备，钙钛矿发光二极管在近10年也取得快速发展，在显示和照明领域具有很好的应用前景。Metal halide perovskite (Perovskite) is a popular material in international research after graphene. It has excellent photoelectric properties, low cost and solution processing, and has been widely studied in the field of optoelectronic device technology; among them, perovskite solar cells Commercial large-scale preparation has been realized, and perovskite light-emitting diodes have also achieved rapid development in the past 10 years, and have good application prospects in the fields of display and lighting.
钙钛矿发光二极管具有的突出优点是色纯度高、溶液法加工。目前，绿光和红光钙钛矿发光二极管的外量子效率已经突破20%，器件寿命也提高到了几百个小时；但是蓝光钙钛矿发光二极管的器件性能还很差，限制了钙钛矿发光二极管的全色显示及其实际应用，因此，寻找合适的方法提高蓝光钙钛矿发光二极管的性能具有重要意义。The outstanding advantages of perovskite light-emitting diodes are high color purity and solution processing. At present, the external quantum efficiency of green and red perovskite light-emitting diodes has exceeded 20%, and the device life has been increased to hundreds of hours; however, the device performance of blue perovskite light-emitting diodes is still very poor, which limits the performance of perovskite light-emitting diodes. The full-color display of light-emitting diodes and its practical application, therefore, it is of great significance to find a suitable method to improve the performance of blue perovskite light-emitting diodes.
制备蓝光钙钛矿常见的方法是在溴体系的钙钛矿中引入一定量的氯离子调节发光光谱，但氯离子的引入会使钙钛矿薄膜的均匀性和结晶性变差，极大地降低器件的发光性能。目前，反溶剂法常被用来改善钙钛矿薄膜的结晶质量，但此法增加了操作复杂性，且难适用于工业上溶液法的大面积器件制备工艺，如印刷和喷墨打印；在器件中引入微纳结构增强光耦合，能提高器件的出光，但加工工艺复杂，增加制造成本；对钙钛矿层进行组分调节，与前两种方法相比更有优势，但实际操作也比较复杂，容易使钙钛矿的发光波长产生大的偏移。The common way to prepare blue-light perovskite is to introduce a certain amount of chloride ions into the perovskite of the bromine system to adjust the luminescence spectrum, but the introduction of chloride ions will make the uniformity and crystallinity of the perovskite film worse, greatly reducing the Luminescent performance of the device. At present, the anti-solvent method is often used to improve the crystallization quality of perovskite films, but this method increases the complexity of the operation, and is difficult to apply to the large-area device preparation process of the industrial solution method, such as printing and inkjet printing; in The introduction of micro-nano structures into the device to enhance optical coupling can improve the light output of the device, but the processing technology is complicated and the manufacturing cost is increased; the composition adjustment of the perovskite layer is more advantageous than the previous two methods, but the actual operation is also relatively Complicated, it is easy to cause a large shift in the emission wavelength of perovskite.
技术问题technical problem
为解决上述问题，本发明的目的是提供一种基于修饰空穴传输层的蓝光钙钛矿发光二极管及其制备方法，适用于溶液法加工的旋涂、刮涂、印刷以及喷墨打印等多种现行的制备工艺技术。In order to solve the above problems, the object of the present invention is to provide a blue-light perovskite light-emitting diode based on a modified hole transport layer and a preparation method thereof, which are suitable for many applications such as spin coating, scraping coating, printing and inkjet printing in solution processing. A current preparation technology.
技术解决方案technical solution
本发明所采取的技术方案是：一种基于修饰空穴传输层的蓝光钙钛矿发光二极管，其空穴传输层为醇胺修饰空穴传输层。进一步的，所述基于修饰空穴传输层的蓝光钙钛矿发光二极管还包括蓝光钙钛矿发光层、电子传输层、阳极和阴极，都为常规技术，根据现有材料以及制备方法得到。The technical scheme adopted in the present invention is: a blue-light perovskite light-emitting diode based on a modified hole transport layer, the hole transport layer of which is an alcohol amine modified hole transport layer. Further, the blue perovskite light-emitting diode based on the modified hole transport layer also includes a blue perovskite light-emitting layer, an electron transport layer, an anode and a cathode, all of which are conventional techniques obtained according to existing materials and preparation methods.
本发明的创造性在于以醇胺修饰空穴传输层作为钙钛矿发光器件中的空穴传输层，其他结构或者组成都是现有技术，所述醇胺优选为丙醇胺（Propanolamine）。优选的，醇胺的体积为空穴传输层原液体积的1~3‰。The inventiveness of the present invention lies in modifying the hole transport layer with alcohol amine as the hole transport layer in the perovskite light-emitting device, other structures or compositions are all prior art, and the alcohol amine is preferably propanolamine (Propanolamine). Preferably, the volume of the alcohol amine is 1-3‰ of the volume of the stock solution of the hole transport layer.
本发明将醇胺与空穴传输层原液按1~3:1000的体积比混合并搅拌均匀，得到修饰的空穴传输层溶液，其中醇胺掺杂浓度为1~3μl/ml。将修饰的空穴传输层溶液根据常规方法制备成膜，作为钙钛矿发光器件中的空穴传输层。In the present invention, the alcohol amine and the stock solution of the hole transport layer are mixed at a volume ratio of 1-3:1000 and stirred evenly to obtain a modified hole transport layer solution, wherein the doping concentration of the alcohol amine is 1-3 μl/ml. The modified hole transport layer solution is prepared into a film according to a conventional method, and used as a hole transport layer in a perovskite light-emitting device.
本发明中，醇胺修饰空穴传输层的厚度为30~40 nm，蓝光钙钛矿发光层厚度为20~25 nm，电子传输层厚度为40~50 nm，LiF厚度为1 nm，Al厚度为90~120 nm。In the present invention, the thickness of the alcohol amine-modified hole transport layer is 30-40 nm, and the thickness of the blue-light perovskite light-emitting layer is 20-25 nm. nm, the thickness of the electron transport layer is 40~50 nm, the thickness of LiF is 1 nm, and the thickness of Al is 90~120 nm.
本发明公开了上述基于修饰空穴传输层的蓝光钙钛矿发光二极管的制备方法，包括以下步骤，将醇胺加入空穴传输层原液中，得到修饰的空穴传输层溶液，然后将修饰的空穴传输层溶液旋涂于阳极表面，退火处理，得到空穴传输层，再制备蓝光钙钛矿发光层、电子传输层和阴极，得到基于修饰空穴传输层的蓝光钙钛矿发光二极管。The invention discloses a preparation method of the above-mentioned blue light perovskite light-emitting diode based on a modified hole transport layer, which includes the following steps: adding alcohol amine into the stock solution of the hole transport layer to obtain a modified hole transport layer solution, and then adding the modified The hole transport layer solution is spin-coated on the surface of the anode, annealed to obtain the hole transport layer, and then the blue perovskite light-emitting layer, electron transport layer and cathode are prepared to obtain the blue perovskite light-emitting diode based on the modified hole transport layer.
本发明公开的空穴传输层原液、蓝光钙钛矿发光层、电子传输层、阳极和阴极都为现有技术，举例而言，空穴传输层原液为PEDOT:PSS原液，蓝光钙钛矿发光层的制备原料包括CsBr、PbBr 2、PbCl 2、KBr、对氟苯乙胺溴（p-f-PEABr）、甲脒氢溴酸盐（FABr），优选的，所述蓝光钙钛矿发光层的组成，CsBr、(PbBr 2+PbCl 2)、KBr、对氟苯乙胺溴（p-f-PEABr）、甲脒氢溴酸盐（FABr）的摩尔比为1.4:1:0.25:0.4:0.15~0.16，进一步优选的，所述PbBr 2、PbCl 2的摩尔比为2~2.2:1；所述电子传输层为TPBi，分别设置ITO和LiF/Al作为钙钛矿发光二极管的阳极和阴极。蓝光钙钛矿发光层、电子传输层、阳极和阴极的制备方法也为现有技术。 The stock solution of the hole transport layer, the blue light perovskite light-emitting layer, the electron transport layer, the anode and the cathode disclosed in the present invention are all prior art. For example, the stock solution of the hole transport layer is a PEDOT:PSS stock solution, and the blue light perovskite emits light. The raw materials for the preparation of the layer include CsBr, PbBr 2 , PbCl 2 , KBr, p-fluorophenethylamine bromide (pf-PEABr), and formamidine hydrobromide (FABr). Preferably, the composition of the blue perovskite light-emitting layer , the molar ratio of CsBr, (PbBr 2 +PbCl 2 ), KBr, p-fluorophenethylamine bromide (pf-PEABr), and formamidine hydrobromide (FABr) is 1.4:1:0.25:0.4:0.15~0.16, Further preferably, the molar ratio of PbBr 2 and PbCl 2 is 2~2.2:1; the electron transport layer is TPBi, and ITO and LiF/Al are respectively set as the anode and cathode of the perovskite light-emitting diode. The preparation methods of the blue light perovskite light-emitting layer, the electron transport layer, the anode and the cathode also belong to the prior art.
有益效果Beneficial effect
本发明有以下优点和有益效果：（1）本发明的修饰材料成本低廉，修饰空穴传输层的方法操作简单，修饰前后不影响器件结构和制备工艺。The present invention has the following advantages and beneficial effects: (1) The modified material of the present invention is low in cost, the method for modifying the hole transport layer is simple to operate, and the device structure and preparation process are not affected before and after modification.
（2）本发明所修饰的空穴传输层，表面存在丙醇胺分子，能提高蓝光钙钛矿薄膜的成膜均匀性，兼容刮涂、印刷和喷墨打印技术工艺，适用于工业上制备大面积钙钛矿发光器件。(2) The hole transport layer modified by the present invention has propanolamine molecules on the surface, which can improve the uniformity of film formation of the blue light perovskite film, is compatible with scraping, printing and inkjet printing technology, and is suitable for industrial preparation Large-area perovskite light-emitting devices.
（3）本发明的修饰材料丙醇胺，能调控钙钛矿结晶，有效钝化钙钛矿缺陷，稳定钙钛矿结构，增强钙钛矿薄膜发光特性和稳定性。所制备的蓝光钙钛矿发光二极管的亮度和外量子效率都得到有效提升，工作寿命达到相关领域研究的先进水平。(3) The modified material propanolamine of the present invention can regulate perovskite crystallization, effectively passivate perovskite defects, stabilize the perovskite structure, and enhance the luminescent properties and stability of perovskite thin films. The brightness and external quantum efficiency of the prepared blue perovskite light-emitting diodes have been effectively improved, and the working life has reached the advanced level of research in related fields.
附图说明Description of drawings
图1为本发明制备的基于修饰空穴传输层的蓝光钙钛矿发光二极管截面扫描电子显微镜测试结果。Fig. 1 is a cross-sectional scanning electron microscope test result of a blue perovskite light-emitting diode based on a modified hole transport layer prepared in the present invention.
图2为本发明实施例1和对比例1中PEDOT:PSS层的接触角测试结果。Fig. 2 is the test result of the contact angle of the PEDOT:PSS layer in Example 1 and Comparative Example 1 of the present invention.
图3是本发明实施例1和对比例1中蓝光钙钛矿发光层的稳态光致发光光谱测试结果。Fig. 3 is the test results of the steady-state photoluminescence spectrum of the blue-light perovskite light-emitting layer in Example 1 and Comparative Example 1 of the present invention.
图4为本发明实施例1和对比例1中蓝光钙钛矿发光层的瞬态荧光寿命测试结果。FIG. 4 shows the test results of the transient fluorescence lifetime of the blue-light perovskite light-emitting layer in Example 1 and Comparative Example 1 of the present invention.
图5为本发明实施例1和对比例1中蓝光钙钛矿发光层的X射线衍射谱图。5 is the X-ray diffraction spectrum of the blue-light perovskite light-emitting layer in Example 1 and Comparative Example 1 of the present invention.
图6为本发明实施例1和对比例1中制备的蓝光钙钛矿发光二极管的电致发光光谱图。FIG. 6 is the electroluminescence spectrum diagram of the blue perovskite light-emitting diodes prepared in Example 1 and Comparative Example 1 of the present invention.
图7为本发明实施例1和对比例1中制备的蓝光钙钛矿发光二极管电压-电流密度曲线和电压-亮度曲线。7 is a voltage-current density curve and a voltage-brightness curve of the blue perovskite light-emitting diodes prepared in Example 1 and Comparative Example 1 of the present invention.
图8为本发明实施例1和对比例1中制备的蓝光钙钛矿发光二极管电流密度-外量子效率曲线。FIG. 8 is the current density-external quantum efficiency curves of the blue perovskite light-emitting diodes prepared in Example 1 and Comparative Example 1 of the present invention.
图9为本发明实施例1和对比例1中制备的蓝光钙钛矿发光二极管在100 cd/m 2的初始发光亮度下随时间衰减的曲线。 Fig. 9 is a curve of decay with time at an initial luminance of 100 cd/m 2 of the blue perovskite light-emitting diodes prepared in Example 1 and Comparative Example 1 of the present invention.
图10为本发明实施例2中制备的大面积（100 mm 2）蓝光钙钛矿发光二极管的工作照片。 FIG. 10 is a working photo of the large-area (100 mm 2 ) blue perovskite light-emitting diode prepared in Example 2 of the present invention.
图11为本发明实施例2中制备的大面积（100 mm 2）蓝光钙钛矿发光二极管的电压-电流密度曲线和电压-亮度曲线。 Fig. 11 is the voltage-current density curve and voltage-brightness curve of the large-area (100 mm 2 ) blue perovskite light-emitting diode prepared in Example 2 of the present invention.
图12为本发明实施例2中制备的大面积（100 mm 2）蓝光钙钛矿发光二极管的电流密度-外量子效率曲线。 Fig. 12 is the current density-external quantum efficiency curve of the large-area (100 mm 2 ) blue perovskite light-emitting diode prepared in Example 2 of the present invention.
本发明的实施方式Embodiments of the present invention
下面结合具体实施例对本发明作进一步的解释和说明。应当理解，以下实施例用于说明本发明，但不用来限制本发明的范围。本发明可采用其它的实施例，并且可以以各种方式被实施或被执行。本发明具体制备方法以及测试方法为本领域常规方法；采用的原料都是现有产品，符合钙钛矿发光二极管的常规要求，比如PEDOT:PSS原液为应用广泛的Al 4083，溶剂为水，固含量为1.5wt.%，PEDOT与PSS的质量比为1∶6；丙醇胺的化学结构式如下：
Figure 352514dest_path_image001
。 The present invention will be further explained and illustrated below in conjunction with specific embodiments. It should be understood that the following examples are used to illustrate the present invention, but not to limit the scope of the present invention. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. The specific preparation method and testing method of the present invention are conventional methods in this field; the raw materials adopted are all existing products, which meet the conventional requirements of perovskite light-emitting diodes, such as PEDOT:PSS stock solution is widely used Al 4083, the solvent is water, solid The content is 1.5wt.%, the mass ratio of PEDOT and PSS is 1:6; the chemical structural formula of propanolamine is as follows:
Figure 352514dest_path_image001
.
作为具体的实施例，以丙醇胺为例，本发明基于修饰空穴传输层的蓝光钙钛矿发光二极管的制备方法为以下详细步骤：S1. 用稀释的Decon水溶液超声清洗阳极基板，之后用去离子水将ITO阳极基板冲洗干净，接着置于乙醇、异丙醇中依次超声清洗5~10分钟，最后用烘箱烘干。As a specific embodiment, taking propanolamine as an example, the preparation method of the present invention based on the blue light perovskite light-emitting diode of the modified hole transport layer is the following detailed steps: S1. Ultrasonic cleaning of the anode substrate with diluted Decon aqueous solution, followed by Rinse the ITO anode substrate with deionized water, then ultrasonically clean it in ethanol and isopropanol for 5-10 minutes, and finally dry it in an oven.
S2. 将丙醇胺添加剂掺入PEDOT:PSS原液中，制备掺杂浓度为1~3μl/ml的PEDOT:PSS溶液。S2. Add the propanolamine additive to the PEDOT:PSS stock solution to prepare a PEDOT:PSS solution with a doping concentration of 1-3 μl/ml.
S3. 将PEDOT:PSS溶液在4000 rpm/min，40 s条件下旋涂，随后在140℃高温退火15分钟，制成空穴传输层。S3. The PEDOT:PSS solution was spin-coated at 4000 rpm/min for 40 s, and then annealed at 140°C for 15 minutes at a high temperature to form a hole transport layer.
S4. 在手套箱（氮气保护）中将CsBr、PbBr 2、PbCl 2、KBr、对氟苯乙胺溴（p-f-PEABr）和甲脒氢溴酸盐（FABr）按所述比例溶于DMSO中，20~30℃加热搅拌3~5小时，制成蓝光钙钛矿溶液，再将其涂在所述S3制备的PEDOT:PSS层上，制成蓝光钙钛矿发光层。 S4. Dissolve CsBr, PbBr 2 , PbCl 2 , KBr, p-fluorophenethylamine bromide (pf-PEABr) and formamidine hydrobromide (FABr) in DMSO in the stated ratio in a glove box (nitrogen protection). , heated and stirred at 20~30°C for 3~5 hours to make a blue light perovskite solution, and then coated it on the PEDOT:PSS layer prepared in S3 to make a blue light perovskite light emitting layer.
S5. 将S4得到的样品薄膜移入真空蒸镀设备中，依次热蒸镀电子传输层和阴极层，制成基于修饰空穴传输层的蓝光钙钛矿发光二极管。S5. Move the sample film obtained in S4 into a vacuum evaporation device, and sequentially thermally evaporate the electron transport layer and the cathode layer to make a blue perovskite light-emitting diode based on the modified hole transport layer.
本发明的创造性不在于制备钙钛矿发光二极管具体原料的选择以及制备参数的限定，在于首次利用醇胺尤其是丙醇胺作为修饰剂掺入空穴传输层，从而有效提高基于该修饰空穴传输层的器件的性能。The inventiveness of the present invention does not lie in the selection of specific raw materials for the preparation of perovskite light-emitting diodes and the limitation of the preparation parameters, but in the first use of alcohol amines, especially propanolamines, as modifiers doped into the hole transport layer, thereby effectively improving the hole transport layer based on the modification. The performance of the device at the transport layer.
实施例 1 一种基于修饰空穴传输层的蓝光钙钛矿发光二极管，其制备方法具体如下：（1）用稀释20倍的Decon水溶液超声清洗ITO阳极基板5分钟，之后用去离子水将ITO阳极基板冲洗干净，接着置于乙醇、异丙醇中依次超声清洗5分钟，最后在烘箱烘干。 Example 1 A blue-light perovskite light-emitting diode based on a modified hole transport layer. The preparation method is as follows: (1) ultrasonically clean the ITO anode substrate with a 20-fold diluted Decon aqueous solution for 5 minutes, and then deionize the ITO with deionized water. The anode substrate was rinsed clean, then placed in ethanol and isopropanol for ultrasonic cleaning for 5 minutes, and finally dried in an oven.
（2）将2μL丙醇胺加入1 mL的PEDOT:PSS原液中，制备掺杂浓度为2μl/ml的PEDOT:PSS溶液。(2) Add 2 μL of propanolamine to 1 mL of PEDOT:PSS stock solution to prepare a PEDOT:PSS solution with a doping concentration of 2 μl/ml.
（3）将上述PEDOT:PSS溶液在4000 rpm/min，40 s条件下旋涂在ITO阳极表面，随后在140℃高温退火15分钟，制成空穴传输层。(3) The above PEDOT:PSS solution was spin-coated on the surface of the ITO anode at 4000 rpm/min for 40 s, followed by high-temperature annealing at 140 °C for 15 minutes to form a hole transport layer.
（4）在手套箱（氮气保护）中将0.282 mmol的CsBr、0.067 mmol的PbBr 2、0.134 mmol的PbCl 2、0.05 mmol的KBr、0.08 mmol的对氟苯乙胺溴（p-f-PEABr）和0.03 mmol的甲脒氢溴酸盐（FABr）溶于1.8 ml的DMSO中，30℃加热搅拌4小时，制成蓝光钙钛矿溶液，以3000 rpm/min的速度旋涂60s，将其涂在上述空穴传输层上，再65℃退火7分钟后制成蓝光钙钛矿发光层。 (4) In a glove box (nitrogen protection), 0.282 mmol of CsBr, 0.067 mmol of PbBr 2 , 0.134 mmol of PbCl 2 , 0.05 mmol of KBr, 0.08 mmol of pf-PEABr and 0.03 Dissolve 1.8 ml of formamidine hydrobromide (FABr) in 1.8 ml of DMSO, heat and stir at 30°C for 4 hours to make a blue light perovskite solution, spin-coat at 3000 rpm/min for 60 seconds, and coat it on the above-mentioned On the hole transport layer, anneal at 65° C. for 7 minutes to form a blue-light perovskite light-emitting layer.
（5）将上述样品薄膜移入真空蒸镀设备中，在蓝光钙钛矿发光层上依次热蒸镀45 nm厚的TPBi、1 nm厚的LiF和100 nm厚的Al，制成发光面积为10 mm 2的蓝光钙钛矿发光二极管；从真空蒸镀设备中取出器件后立即在手套箱中进行封装。 (5) Move the above sample film into the vacuum evaporation equipment, and sequentially thermally evaporate 45 nm thick TPBi, 1 nm thick LiF and 100 nm thick Al on the blue perovskite light-emitting layer to make a light-emitting area of 10 mm 2 blue light-emitting perovskite light-emitting diodes; the device was packaged in a glove box immediately after taking it out of the vacuum evaporation equipment.
对比例 1 ：本对比例的其他步骤与实施例1完全一致，区别在于：PEDOT:PSS原液无需掺杂处理。如下：（1）用稀释20倍的Decon水溶液超声清洗ITO阳极基板5分钟，之后用去离子水将ITO阳极基板冲洗干净，接着置于乙醇、异丙醇中依次超声清洗5分钟，最后在烘箱烘干。 Comparative example 1 : other steps of this comparative example are completely consistent with embodiment 1, difference is: PEDOT:PSS stoste solution does not need doping treatment. As follows: (1) Ultrasonic clean the ITO anode substrate with a 20-fold diluted Decon aqueous solution for 5 minutes, then rinse the ITO anode substrate with deionized water, then place it in ethanol and isopropanol for 5 minutes, and finally place it in an oven drying.
（2）将PEDOT:PSS原液在4000 rpm/min，40 s条件下旋涂在ITO阳极表面，随后在140℃高温退火15分钟，制成空穴传输层。(2) The PEDOT:PSS stock solution was spin-coated on the surface of the ITO anode at 4000 rpm/min for 40 s, and then annealed at 140 °C for 15 minutes to form a hole transport layer.
（3）在手套箱（氮气保护）中将0.282 mmol的CsBr、0.067 mmol的PbBr 2、0.134 mmol的PbCl 2、0.05 mmol的KBr、0.08 mmol的对氟苯乙胺溴（p-f-PEABr）和0.03 mmol的甲脒氢溴酸盐（FABr）溶于1.8 ml的DMSO中，30℃加热搅拌4小时，制成蓝光钙钛矿溶液，以3000 rpm/min的速度旋涂60s，将其涂在上述空穴传输层上，再65℃退火7分钟后制成蓝光钙钛矿发光层。 (3) In a glove box (nitrogen protection), 0.282 mmol of CsBr, 0.067 mmol of PbBr 2 , 0.134 mmol of PbCl 2 , 0.05 mmol of KBr, 0.08 mmol of pf-PEABr and 0.03 Dissolve 1.8 ml of formamidine hydrobromide (FABr) in 1.8 ml of DMSO, heat and stir at 30°C for 4 hours to make a blue light perovskite solution, spin-coat at 3000 rpm/min for 60 seconds, and coat it on the above-mentioned On the hole transport layer, anneal at 65° C. for 7 minutes to form a blue-light perovskite light-emitting layer.
（4）将上述样品薄膜移入真空蒸镀设备中，在蓝光钙钛矿发光层上依次热蒸镀45 nm厚的TPBi、1 nm厚的LiF和100 nm厚的Al，制成发光面积为10 mm 2的蓝光钙钛矿发光二极管；从真空蒸镀设备中取出器件后立即在手套箱中进行封装。 (4) Move the above sample film into the vacuum evaporation equipment, and sequentially thermally evaporate 45 nm thick TPBi, 1 nm thick LiF and 100 nm thick Al on the blue perovskite light-emitting layer to make a light-emitting area of 10 mm 2 blue light-emitting perovskite light-emitting diodes; the device was packaged in a glove box immediately after taking it out of the vacuum evaporation equipment.
性能测试结果：实施例1制备的基于修饰空穴传输层的蓝光钙钛矿发光二极管的截面扫描电子显微镜图如图1所示，空穴传输层、蓝光钙钛矿发光层的厚度分别为34nm、24 nm，其他实施例、对比例一致。 Performance test results: The cross-sectional scanning electron microscope image of the blue perovskite light-emitting diode based on the modified hole transport layer prepared in Example 1 is shown in Figure 1. The thicknesses of the hole transport layer and the blue perovskite light-emitting layer are respectively 34nm , 24 nm, other embodiments and comparative examples are consistent.
接触角测试是通过接触角测试仪（DataPhysics Instruments GmbH）测量的；稳态光致发光光谱是用FluoroMax-4荧光光谱仪 (Horiba Jobin Yvon) 测量的；瞬态荧光寿命测试是    使用Quantaurus-Tau荧光寿命光谱仪（C11367-32，Hamamatsu Photonics）测量的；钙钛矿薄膜的X射线衍射谱图是使用衍射仪 (D8 Discover)的平面模式记录的；蓝光钙钛矿发光二极管器件性能测试是使用计算机控制的可编程电源（Keithley 2400 型）和一个亮度计/光谱仪（PhotoResearch PR655）同时测量器件的电流密度-电压-亮度（J-V-L）特性和电致发光光谱，测试系统根据测量的 J-V-L 特性和具有朗伯分布的电致发光光谱，自动给出器件的外量子效率（EQE）。The contact angle test was measured by a contact angle tester (DataPhysics Instruments GmbH); the steady-state photoluminescence spectrum was measured by a FluoroMax-4 fluorescence spectrometer (Horiba Jobin Yvon); the transient fluorescence lifetime test was Using a Quantaurus-Tau fluorescence lifetime spectrometer (C11367-32, Hamamatsu Photonics); the X-ray diffraction spectrum of the perovskite film was obtained using a diffractometer (D8 Discover) planar mode recording; blue light perovskite light-emitting diode device performance test is using a computer-controlled programmable power supply (Keithley 2400) and a photometer/spectrometer (PhotoResearch PR655) Simultaneously measure the current density-voltage-luminance (J-V-L) characteristics and electroluminescence spectrum of the device, the test system is based on the measured The J-V-L characteristics and the electroluminescence spectrum with Lambertian distribution automatically give the external quantum efficiency (EQE) of the device.
如图2所示，实施例1丙醇胺修饰后的PEDOT:PSS层接触角明显小于对比例1中未经修饰的PEDOT:PSS层，表明本发明公开的空穴传输层具有好的亲水性。如图3和图4所示，经过丙醇胺修饰，蓝光钙钛矿发光层光致发光强度增强了一倍左右，载流子寿命也大大增长，表明丙醇胺修饰能钝化钙钛矿层，抑制非辐射复合。如图5所示，图中带括号的数字表示晶面，经过丙醇胺修饰，蓝光钙钛矿发光层的结晶性增强。As shown in Figure 2, the contact angle of the PEDOT:PSS layer modified by propanolamine in Example 1 is significantly smaller than that of the unmodified PEDOT:PSS layer in Comparative Example 1, indicating that the hole transport layer disclosed by the present invention has good hydrophilicity sex. As shown in Figure 3 and Figure 4, after propanolamine modification, the photoluminescence intensity of the blue perovskite light-emitting layer is about doubled, and the carrier lifetime is also greatly increased, indicating that propanolamine modification can passivate the perovskite layer , to suppress nonradiative recombination. As shown in Figure 5, the numbers in parentheses in the figure indicate crystal planes, and after propanolamine modification, the crystallinity of the blue perovskite light-emitting layer is enhanced.
由图6～9得到实施例1和对比例1中蓝光钙钛矿发光二极管的性能参数如下表1所示：
Figure 482144dest_path_image002
。 From Figures 6 to 9, the performance parameters of the blue perovskite light-emitting diodes in Example 1 and Comparative Example 1 are shown in Table 1 below:
Figure 482144dest_path_image002
.
如表1所示，经过丙醇胺修饰，器件开启电压从4 V降到3.4 V，表明器件中载流子注入平衡改善；本实例1制备的基于修饰空穴传输层的蓝光钙钛矿发光二极管发光波长为479 nm，最高亮度为620 cd/m 2，最高外量子效率为6.6%，在100 cd/m 2的初始亮度下的T 50工作寿命（亮度降到一半所用的时间）长达420 s。 As shown in Table 1, after propanolamine modification, the turn-on voltage of the device dropped from 4 V to 3.4 V, indicating that the carrier injection balance in the device was improved; the blue perovskite based on the modified hole transport layer prepared in this example 1 emits light The diode emits at a wavelength of 479 nm, the highest brightness is 620 cd/m 2 , the highest external quantum efficiency is 6.6%, and the T 50 working life (the time it takes for the brightness to drop to half) at an initial brightness of 100 cd/m 2 is as long as 420 s.
实施例 2 ：本实施例与实施例1的区别在于：步骤（1）中，所用的ITO阳极基板的有效面积不同，最终制成器件的发光面积大小不同。本实施例中基于修饰空穴传输层的蓝光钙钛矿发光二极管的发光面积是100 mm 2。其余参数都一样。如下：（1）用稀释20倍的Decon水溶液超声清洗ITO阳极基板5分钟，之后用去离子水将ITO阳极基板冲洗干净，接着置于乙醇、异丙醇中依次超声清洗5分钟，最后在烘箱烘干。 Embodiment 2 : The difference between this embodiment and Embodiment 1 is that in step (1), the effective area of the ITO anode substrate used is different, and the size of the light emitting area of the final device is different. In this embodiment, the light emitting area of the blue perovskite light emitting diode based on the modified hole transport layer is 100 mm 2 . The rest of the parameters are the same. As follows: (1) Ultrasonic clean the ITO anode substrate with a 20-fold diluted Decon aqueous solution for 5 minutes, then rinse the ITO anode substrate with deionized water, then place it in ethanol and isopropanol for 5 minutes, and finally place it in an oven drying.
（2）将2μL丙醇胺加入1mL的PEDOT:PSS原液中，制备掺杂浓度为2 μl/ml的PEDOT:PSS溶液。(2) Add 2 μL of propanolamine to 1 mL of PEDOT:PSS stock solution to prepare a PEDOT:PSS solution with a doping concentration of 2 μl/ml.
（3）将上述PEDOT:PSS溶液在4000 rpm/min，40 s条件下旋涂在ITO阳极表面，随后在140℃高温退火15分钟，制成空穴传输层。(3) The above PEDOT:PSS solution was spin-coated on the surface of the ITO anode at 4000 rpm/min for 40 s, followed by high-temperature annealing at 140 °C for 15 minutes to form a hole transport layer.
（4）在手套箱（氮气保护）中将0.282 mmol的CsBr、0.067 mmol的PbBr 2、0.134 mmol的PbCl 2、0.05 mmol的KBr、0.08 mmol的对氟苯乙胺溴（p-f-PEABr）和0.03 mmol的甲脒氢溴酸盐（FABr）溶于1.8 ml的DMSO中，30℃加热搅拌4小时，制成蓝光钙钛矿溶液，以3000 rpm/min的速度旋涂60s，将其涂在上述空穴传输层上，再65℃退火7分钟后制成蓝光钙钛矿发光层。 (4) In a glove box (nitrogen protection), 0.282 mmol of CsBr, 0.067 mmol of PbBr 2 , 0.134 mmol of PbCl 2 , 0.05 mmol of KBr, 0.08 mmol of pf-PEABr and 0.03 Dissolve 1.8 ml of formamidine hydrobromide (FABr) in 1.8 ml of DMSO, heat and stir at 30°C for 4 hours to make a blue light perovskite solution, spin-coat at 3000 rpm/min for 60 seconds, and coat it on the above-mentioned On the hole transport layer, anneal at 65° C. for 7 minutes to form a blue-light perovskite light-emitting layer.
（5）将上述样品薄膜移入真空蒸镀设备中，在蓝光钙钛矿发光层上依次热蒸镀45 nm厚的TPBi、1 nm厚的LiF和100 nm厚的Al，制成发光面积为100 mm 2的蓝光钙钛矿发光二极管；从真空蒸镀设备中取出器件后立即在手套箱中进行封装。 (5) Move the above sample film into the vacuum evaporation equipment, and sequentially thermally evaporate 45 nm thick TPBi, 1 nm thick LiF and 100 nm thick Al on the blue perovskite light-emitting layer to make a light-emitting area of 100 mm 2 blue light-emitting perovskite light-emitting diodes; the device was packaged in a glove box immediately after taking it out of the vacuum evaporation equipment.
本实施例的器件工作照片如图10所示，发光面积是个1 cm*1 cm的正方形。本实施例的器件性能参数如图11和图12所示，器件最高亮度为627 cd/m 2，最高外量子效率为5.1%。 The working photo of the device in this embodiment is shown in FIG. 10 , and the light emitting area is a square of 1 cm*1 cm. The performance parameters of the device in this embodiment are shown in Figure 11 and Figure 12, the highest brightness of the device is 627 cd/m 2 , and the highest external quantum efficiency is 5.1%.
对比例 2 一种基于修饰空穴传输层的蓝光钙钛矿发光二极管，其制备方法具体如下：（1）用稀释20倍的Decon水溶液超声清洗ITO阳极基板5分钟，之后用去离子水将ITO阳极基板冲洗干净，接着置于乙醇、异丙醇中依次超声清洗5分钟，最后在烘箱烘干。 Comparative Example 2 A blue-light perovskite light-emitting diode based on a modified hole transport layer. The preparation method is as follows: (1) ultrasonically clean the ITO anode substrate with 20 times diluted Decon aqueous solution for 5 minutes, and then deionize the ITO with deionized water. The anode substrate was rinsed clean, then placed in ethanol and isopropanol for ultrasonic cleaning for 5 minutes, and finally dried in an oven.
（2）将2 mg醋酸锌（Zn(CH 3COO) 2）加入1 mL的PEDOT:PSS原液中，制备PEDOT:PSS溶液。 (2) Add 2 mg of zinc acetate (Zn(CH 3 COO) 2 ) to 1 mL of PEDOT:PSS stock solution to prepare PEDOT:PSS solution.
（3）将上述PEDOT:PSS溶液在4000 rpm/min，40 s条件下旋涂在ITO阳极表面，随后在140℃高温退火15分钟，制成空穴传输层。(3) The above PEDOT:PSS solution was spin-coated on the surface of the ITO anode at 4000 rpm/min for 40 s, followed by high-temperature annealing at 140 °C for 15 minutes to form a hole transport layer.
（4）在手套箱（氮气保护）中将0.282 mmol的CsBr、0.067 mmol的PbBr 2、0.134 mmol的PbCl 2、0.05 mmol的KBr、0.08 mmol的对氟苯乙胺溴（p-f-PEABr）和0.03 mmol的甲脒氢溴酸盐（FABr）溶于1.8 ml的DMSO中，30℃加热搅拌4小时，制成蓝光钙钛矿溶液，以3000 rpm/min的速度旋涂60s，将其涂在上述空穴传输层上，再65℃退火7分钟后制成蓝光钙钛矿发光层。 (4) In a glove box (nitrogen protection), 0.282 mmol of CsBr, 0.067 mmol of PbBr 2 , 0.134 mmol of PbCl 2 , 0.05 mmol of KBr, 0.08 mmol of pf-PEABr and 0.03 Dissolve 1.8 ml of formamidine hydrobromide (FABr) in 1.8 ml of DMSO, heat and stir at 30°C for 4 hours to make a blue light perovskite solution, spin-coat at 3000 rpm/min for 60 seconds, and coat it on the above-mentioned On the hole transport layer, anneal at 65° C. for 7 minutes to form a blue-light perovskite light-emitting layer.
（5）将上述样品薄膜移入真空蒸镀设备中，在蓝光钙钛矿发光层上依次热蒸镀45 nm厚的TPBi、1 nm厚的LiF和100 nm厚的Al，制成发光面积为10 mm 2的蓝光钙钛矿发光二极管；从真空蒸镀设备中取出器件后立即在手套箱中进行封装。 (5) Move the above sample film into the vacuum evaporation equipment, and sequentially thermally evaporate 45 nm thick TPBi, 1 nm thick LiF and 100 nm thick Al on the blue perovskite light-emitting layer to make a light-emitting area of 10 mm 2 blue light-emitting perovskite light-emitting diodes; the device was packaged in a glove box immediately after taking it out of the vacuum evaporation equipment.
器件最高亮度为268 cd/m 2，最高外量子效率为3.6 %，发光波长为479 nm。 The highest brightness of the device is 268 cd/m 2 , the highest external quantum efficiency is 3.6%, and the emission wavelength is 479 nm.
实施例 3 一种基于修饰空穴传输层的蓝光钙钛矿发光二极管，其制备方法具体如下：（1）用稀释20倍的Decon水溶液超声清洗ITO阳极基板5分钟，之后用去离子水将ITO阳极基板冲洗干净，接着置于乙醇、异丙醇中依次超声清洗5分钟，最后在烘箱烘干。 Example 3 A blue-light perovskite light-emitting diode based on a modified hole transport layer. The preparation method is as follows: (1) ultrasonically clean the ITO anode substrate with a 20-fold diluted Decon aqueous solution for 5 minutes, and then deionize the ITO with deionized water. The anode substrate was rinsed clean, then placed in ethanol and isopropanol for ultrasonic cleaning for 5 minutes, and finally dried in an oven.
（2）将1μL丙醇胺加入1L的PEDOT:PSS原液中，制备掺杂浓度为1μl/ml的PEDOT:PSS溶液。(2) Add 1 μL of propanolamine to 1 L of PEDOT:PSS stock solution to prepare a PEDOT:PSS solution with a doping concentration of 1 μl/ml.
（3）将上述PEDOT:PSS溶液在4000 rpm/min，40 s条件下旋涂在ITO阳极表面，随后在140℃高温退火15分钟，制成空穴传输层。(3) The above PEDOT:PSS solution was spin-coated on the surface of the ITO anode at 4000 rpm/min for 40 s, followed by high-temperature annealing at 140 °C for 15 minutes to form a hole transport layer.
（4）在手套箱（氮气保护）中将0.282 mmol的CsBr、0.067 mmol的PbBr 2、0.134 mmol的PbCl 2、0.05 mmol的KBr、0.08 mmol的对氟苯乙胺溴（p-f-PEABr）和0.03 mmol的甲脒氢溴酸盐（FABr）溶于1.8 ml的DMSO中，30℃加热搅拌4小时，制成蓝光钙钛矿溶液，以3000 rpm/min的速度旋涂60s，将其涂在上述空穴传输层上，再65℃退火7分钟后制成蓝光钙钛矿发光层。 (4) In a glove box (nitrogen protection), 0.282 mmol of CsBr, 0.067 mmol of PbBr 2 , 0.134 mmol of PbCl 2 , 0.05 mmol of KBr, 0.08 mmol of pf-PEABr and 0.03 Dissolve 1.8 ml of formamidine hydrobromide (FABr) in 1.8 ml of DMSO, heat and stir at 30°C for 4 hours to make a blue light perovskite solution, spin-coat at 3000 rpm/min for 60 seconds, and coat it on the above-mentioned On the hole transport layer, anneal at 65° C. for 7 minutes to form a blue-light perovskite light-emitting layer.
（5）将上述样品薄膜移入真空蒸镀设备中，在蓝光钙钛矿发光层上依次热蒸镀45 nm厚的TPBi、1 nm厚的LiF和100 nm厚的Al，制成发光面积为10 mm 2的蓝光钙钛矿发光二极管；从真空蒸镀设备中取出器件后立即在手套箱中进行封装。 (5) Move the above sample film into the vacuum evaporation equipment, and sequentially thermally evaporate 45 nm thick TPBi, 1 nm thick LiF and 100 nm thick Al on the blue perovskite light-emitting layer to make a light-emitting area of 10 mm 2 blue light-emitting perovskite light-emitting diodes; the device was packaged in a glove box immediately after taking it out of the vacuum evaporation equipment.
器件最高亮度为473 cd/m 2，最高外量子效率为4.9%，发光波长为481nm。 The highest brightness of the device is 473 cd/m 2 , the highest external quantum efficiency is 4.9%, and the emission wavelength is 481nm.
实施例 4 一种基于修饰P EDOT:PSS层的蓝光钙钛矿发光二极管，其制备方法具体如下：（1）用稀释20倍的Decon水溶液超声清洗ITO阳极基板5分钟，之后用去离子水将ITO阳极基板冲洗干净，接着置于乙醇、异丙醇中依次超声清洗5分钟，最后在烘箱烘干。 Example 4 A blue-light perovskite light-emitting diode based on a modified PEDOT:PSS layer. The preparation method is as follows: (1) Ultrasonic cleaning of the ITO anode substrate with 20-fold diluted Decon aqueous solution for 5 minutes, and then deionized water The ITO anode substrate was rinsed clean, then placed in ethanol and isopropanol for ultrasonic cleaning for 5 minutes, and finally dried in an oven.
（2）将3μL丙醇胺加入1L的PEDOT:PSS原液中，制备掺杂浓度为3μl/ml的PEDOT:PSS溶液。(2) Add 3 μL of propanolamine to 1 L of PEDOT:PSS stock solution to prepare a PEDOT:PSS solution with a doping concentration of 3 μl/ml.
（3）将上述PEDOT:PSS溶液在4000 rpm/min，40 s条件下旋涂在ITO阳极表面，随后在140℃高温退火15分钟，制成空穴传输层。(3) The above PEDOT:PSS solution was spin-coated on the surface of the ITO anode at 4000 rpm/min for 40 s, followed by high-temperature annealing at 140 °C for 15 minutes to form a hole transport layer.
（4）在手套箱（氮气保护）中将0.282 mmol的CsBr、0.067 mmol的PbBr 2、0.134 mmol的PbCl 2、0.05 mmol的KBr、0.08 mmol的对氟苯乙胺溴（p-f-PEABr）和0.03 mmol的甲脒氢溴酸盐（FABr）溶于1.8 ml的DMSO中，30℃加热搅拌4小时，制成蓝光钙钛矿溶液，以3000 rpm/min的速度旋涂60s，将其涂在上述空穴传输层上，再65℃退火7分钟后制成蓝光钙钛矿发光层。 (4) In a glove box (nitrogen protection), 0.282 mmol of CsBr, 0.067 mmol of PbBr 2 , 0.134 mmol of PbCl 2 , 0.05 mmol of KBr, 0.08 mmol of pf-PEABr and 0.03 Dissolve 1.8 ml of formamidine hydrobromide (FABr) in 1.8 ml of DMSO, heat and stir at 30°C for 4 hours to make a blue light perovskite solution, spin-coat at 3000 rpm/min for 60 seconds, and coat it on the above-mentioned On the hole transport layer, anneal at 65° C. for 7 minutes to form a blue-light perovskite light-emitting layer.
（5）将上述样品薄膜移入真空蒸镀设备中，在蓝光钙钛矿发光层上依次热蒸镀45 nm厚的TPBi、1 nm厚的LiF和100 nm厚的Al，制成发光面积为10 mm 2的蓝光钙钛矿发光二极管；从真空蒸镀设备中取出器件后立即在手套箱中进行封装。 (5) Move the above sample film into the vacuum evaporation equipment, and sequentially thermally evaporate 45 nm thick TPBi, 1 nm thick LiF and 100 nm thick Al on the blue perovskite light-emitting layer to make a light-emitting area of 10 mm 2 blue light-emitting perovskite light-emitting diodes; the device was packaged in a glove box immediately after taking it out of the vacuum evaporation equipment.
器件最高亮度为383 cd/m 2，最高外量子效率为4.3%，发光波长为476 nm。 The highest brightness of the device is 383 cd/m 2 , the highest external quantum efficiency is 4.3%, and the emission wavelength is 476 nm.
实施例 5 一种基于修饰P EDOT:PSS层的蓝光钙钛矿发光二极管，其制备方法具体如下：（1）用稀释20倍的Decon水溶液超声清洗ITO阳极基板5分钟，之后用去离子水将ITO阳极基板冲洗干净，接着置于乙醇、异丙醇中依次超声清洗5分钟，最后在烘箱烘干。 Example 5 A blue-light perovskite light-emitting diode based on a modified PEDOT:PSS layer. The preparation method is as follows: (1) Ultrasonic cleaning of the ITO anode substrate with 20-fold diluted Decon aqueous solution for 5 minutes, and then deionized water The ITO anode substrate was rinsed clean, then placed in ethanol and isopropanol for ultrasonic cleaning for 5 minutes, and finally dried in an oven.
（2）将4μL丙醇胺加入1L的PEDOT:PSS原液中，制备掺杂浓度为4μl/ml的PEDOT:PSS溶液。(2) Add 4 μL of propanolamine to 1 L of PEDOT:PSS stock solution to prepare a PEDOT:PSS solution with a doping concentration of 4 μl/ml.
（3）将上述PEDOT:PSS溶液在4000 rpm/min，40 s条件下旋涂在ITO阳极表面，随后在140℃高温退火15分钟，制成空穴传输层。(3) The above PEDOT:PSS solution was spin-coated on the surface of the ITO anode at 4000 rpm/min for 40 s, followed by high-temperature annealing at 140 °C for 15 minutes to form a hole transport layer.
（4）在手套箱（氮气保护）中将0.282 mmol的CsBr、0.067 mmol的PbBr 2、0.134 mmol的PbCl 2、0.05 mmol的KBr、0.08 mmol的对氟苯乙胺溴（p-f-PEABr）和0.03 mmol的甲脒氢溴酸盐（FABr）溶于1.8 ml的DMSO中，30℃加热搅拌4小时，制成蓝光钙钛矿溶液，以3000 rpm/min的速度旋涂60s，将其涂在上述空穴传输层上，再65℃退火7分钟后制成蓝光钙钛矿发光层。 (4) In a glove box (nitrogen protection), 0.282 mmol of CsBr, 0.067 mmol of PbBr 2 , 0.134 mmol of PbCl 2 , 0.05 mmol of KBr, 0.08 mmol of pf-PEABr and 0.03 Dissolve 1.8 ml of formamidine hydrobromide (FABr) in 1.8 ml of DMSO, heat and stir at 30°C for 4 hours to make a blue light perovskite solution, spin-coat at 3000 rpm/min for 60 seconds, and coat it on the above-mentioned On the hole transport layer, anneal at 65° C. for 7 minutes to form a blue-light perovskite light-emitting layer.
（5）将上述样品薄膜移入真空蒸镀设备中，在蓝光钙钛矿发光层上依次热蒸镀45 nm厚的TPBi、1 nm厚的LiF和100 nm厚的Al，制成发光面积为10 mm 2的蓝光钙钛矿发光二极管；从真空蒸镀设备中取出器件后立即在手套箱中进行封装。 (5) Move the above sample film into the vacuum evaporation equipment, and sequentially thermally evaporate 45 nm thick TPBi, 1 nm thick LiF and 100 nm thick Al on the blue perovskite light-emitting layer to make a light-emitting area of 10 mm 2 blue light-emitting perovskite light-emitting diodes; the device was packaged in a glove box immediately after taking it out of the vacuum evaporation equipment.
器件最高亮度为256 cd/m 2，最高外量子效率为4.0%，发光波长为473 nm。 The highest brightness of the device is 256 cd/m 2 , the highest external quantum efficiency is 4.0%, and the emission wavelength is 473 nm.
除了旋涂和热蒸镀，以上各层结构的具体制作工艺也可选择溶液法刮涂、印刷、喷墨打印等公知方法；本领域的技术人员容易理解，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。In addition to spin coating and thermal evaporation, the specific manufacturing process of each layer structure above can also choose known methods such as solution method scraping coating, printing, inkjet printing; those skilled in the art can easily understand that the above is only a specific example of the present invention. The embodiment is only used to limit the protection scope of the present invention, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (10)

  1. 一种基于修饰空穴传输层的蓝光钙钛矿发光二极管，其特征在于，所述基于修饰空穴传输层的蓝光钙钛矿发光二极管的空穴传输层为醇胺修饰空穴传输层。A blue perovskite light emitting diode based on a modified hole transport layer, characterized in that the hole transport layer of the blue perovskite light emitting diode based on a modified hole transport layer is an alcohol amine modified hole transport layer.
  2. 根据权利要求1所述基于修饰空穴传输层的蓝光钙钛矿发光二极管，其特征在于，所述基于修饰空穴传输层的蓝光钙钛矿发光二极管还包括蓝光钙钛矿发光层、电子传输层、阳极和阴极。The blue light perovskite light emitting diode based on the modified hole transport layer according to claim 1, wherein the blue light perovskite light emitting diode based on the modified hole transport layer also includes a blue light perovskite light emitting layer, an electron transport layer, anode and cathode.
  3. 根据权利要求1所述基于修饰空穴传输层的蓝光钙钛矿发光二极管，其特征在于，所述醇胺为丙醇胺。The blue perovskite light-emitting diode based on the modified hole transport layer according to claim 1, wherein the alcohol amine is propanolamine.
  4. 根据权利要求1所述基于修饰空穴传输层的蓝光钙钛矿发光二极管，其特征在于，将醇胺与空穴传输层原液按1~3:1000的体积比混合并搅拌均匀，得到修饰的空穴传输层溶液，再将修饰的空穴传输层溶液制备成膜，作为基于修饰空穴传输层的蓝光钙钛矿发光二极管的空穴传输层。The blue perovskite light-emitting diode based on the modified hole transport layer according to claim 1, wherein the alcohol amine and the hole transport layer stock solution are mixed and stirred evenly at a volume ratio of 1 to 3:1000 to obtain a modified The hole transport layer solution, and then prepare the modified hole transport layer solution into a film, as the hole transport layer of the blue light perovskite light-emitting diode based on the modified hole transport layer.
  5. 根据权利要求1所述基于修饰空穴传输层的蓝光钙钛矿发光二极管，其特征在于，醇胺修饰空穴传输层的厚度为30~40 nm，蓝光钙钛矿发光层厚度为20~25 nm。According to the blue light perovskite light emitting diode based on the modified hole transport layer according to claim 1, it is characterized in that the thickness of the alcohol amine modified hole transport layer is 30~40 nm, and the thickness of the blue light perovskite light emitting layer is 20~25 nm. nm.
  6. 权利要求1所述基于修饰空穴传输层的蓝光钙钛矿发光二极管的制备方法，其特征在于，包括以下步骤，将醇胺加入空穴传输层原液中，得到修饰的空穴传输层溶液，然后将修饰的空穴传输层溶液涂于阳极表面，退火处理，得到空穴传输层，再制备蓝光钙钛矿发光层、电子传输层和阴极，得到基于修饰空穴传输层的蓝光钙钛矿发光二极管。The preparation method of the blue-light perovskite light-emitting diode based on the modified hole transport layer according to claim 1, characterized in that it comprises the following steps, adding alcohol amine to the stock solution of the hole transport layer to obtain a modified hole transport layer solution, Then apply the modified hole transport layer solution on the surface of the anode, and anneal to obtain the hole transport layer, and then prepare the blue light perovskite light-emitting layer, electron transport layer and cathode to obtain the blue light perovskite based on the modified hole transport layer led.
  7. 根据权利要求6所述基于修饰空穴传输层的蓝光钙钛矿发光二极管的制备方法，其特征在于，醇胺的体积为空穴传输层原液体积的1~3‰。According to the preparation method of the blue-light perovskite light-emitting diode based on the modified hole transport layer according to claim 6, it is characterized in that the volume of the alcohol amine is 1-3‰ of the volume of the stock solution of the hole transport layer.
  8. 一种蓝光钙钛矿发光二极管用空穴传输层溶液，其特征在于，包括醇胺与空穴传输层原液。A solution for a hole transport layer for a blue-light perovskite light-emitting diode, which is characterized in that it includes alcohol amine and a stock solution of the hole transport layer.
  9. 一种蓝光钙钛矿发光二极管用空穴传输层，其特征在于，将醇胺与空穴传输层原液按1~3:1000的体积比混合并搅拌均匀，得到修饰的空穴传输层溶液，再将修饰的空穴传输层溶液制备成膜，作为蓝光钙钛矿发光二极管用空穴传输层。A hole transport layer for a blue light perovskite light-emitting diode, characterized in that the alcohol amine and the hole transport layer stock solution are mixed and stirred uniformly at a volume ratio of 1 to 3:1000 to obtain a modified hole transport layer solution, Then the modified hole transport layer solution is prepared into a film, which is used as the hole transport layer for the blue light perovskite light-emitting diode.
  10. 醇胺在制备蓝光钙钛矿发光二极管用空穴传输层中的应用；或者醇胺在制备蓝光钙钛矿发光二极管中的应用。The application of alcohol amine in the preparation of the hole transport layer for the blue light perovskite light-emitting diode; or the application of the alcohol amine in the preparation of the blue light perovskite light-emitting diode.
PCT/CN2021/108008 2021-07-22 2021-07-22 Blue-light perovskite light-emitting diode based on modified hole transport layer and preparation method therefor WO2023000280A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/108008 WO2023000280A1 (en) 2021-07-22 2021-07-22 Blue-light perovskite light-emitting diode based on modified hole transport layer and preparation method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/108008 WO2023000280A1 (en) 2021-07-22 2021-07-22 Blue-light perovskite light-emitting diode based on modified hole transport layer and preparation method therefor

Publications (1)

Publication Number Publication Date
WO2023000280A1 true WO2023000280A1 (en) 2023-01-26

Family

ID=84980318

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/108008 WO2023000280A1 (en) 2021-07-22 2021-07-22 Blue-light perovskite light-emitting diode based on modified hole transport layer and preparation method therefor

Country Status (1)

Country Link
WO (1) WO2023000280A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170358399A1 (en) * 2016-06-08 2017-12-14 Ricoh Company, Ltd. Tertiary amine compound, photoelectric conversion element, and solar cell
CN110739411A (en) * 2019-10-25 2020-01-31 中国科学院长春光学精密机械与物理研究所 preparation method of perovskite light-emitting diode capable of improving performance
CN111883679A (en) * 2020-07-04 2020-11-03 苏州大学 Blue-light perovskite light-emitting diode based on total bromine proportion and preparation method thereof
CN113594383A (en) * 2021-07-21 2021-11-02 苏州大学 Blue-light perovskite light-emitting diode based on modified hole transport layer and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170358399A1 (en) * 2016-06-08 2017-12-14 Ricoh Company, Ltd. Tertiary amine compound, photoelectric conversion element, and solar cell
CN110739411A (en) * 2019-10-25 2020-01-31 中国科学院长春光学精密机械与物理研究所 preparation method of perovskite light-emitting diode capable of improving performance
CN111883679A (en) * 2020-07-04 2020-11-03 苏州大学 Blue-light perovskite light-emitting diode based on total bromine proportion and preparation method thereof
CN113594383A (en) * 2021-07-21 2021-11-02 苏州大学 Blue-light perovskite light-emitting diode based on modified hole transport layer and preparation method thereof

Similar Documents

Publication Publication Date Title
Wu et al. Improved performance and stability of all‐inorganic perovskite light‐emitting diodes by antisolvent vapor treatment
CN108281572B (en) Perovskite light emitting diode of the compound containing inferior ethoxyl and preparation method thereof
CN107978688B (en) Electroluminescent LED and preparation method based on vulcanized lead cladding perovskite quantum dot
CN113611807B (en) Blue-light perovskite light-emitting diode and preparation method thereof
KR20070036835A (en) Method for preparation of organic light emitting devices comprising inorganic buffer layer
Jiang et al. Interface and bulk controlled perovskite nanocrystal growth for high brightness light-emitting diodes
CN109860379B (en) All-inorganic perovskite quantum dot multicolor luminescent film and preparation method thereof
Huang et al. Improved phase purity and film quality in quasi-2D perovskite light-emitting diodes by an additive with the trimethacrylate group
Ou et al. Ampholytic interface induced in situ growth of CsPbBr 3 for highly efficient perovskite light-emitting diodes
CN113991045A (en) Pure blue light perovskite luminescent layer, preparation method thereof and light emitting diode
CN111785846A (en) Green-light perovskite light-emitting diode based on surface post-treatment process and preparation
CN113594383A (en) Blue-light perovskite light-emitting diode based on modified hole transport layer and preparation method thereof
Liu et al. Effect of chloride Ion concentrations on luminescence peak blue shift of light-emitting diode using anti-solvent extraction of quasi-two-dimensional perovskite
WO2023000280A1 (en) Blue-light perovskite light-emitting diode based on modified hole transport layer and preparation method therefor
CN116828942A (en) Preparation method of blue-light perovskite film, blue-light perovskite film and light-emitting device
CN106784391A (en) Quantum dot light emitting device and preparation method thereof, liquid crystal display device
CN112117386B (en) PEACl-based modified CsPb (Cl/Br)3Quantum dot electroluminescent LED and preparation method thereof
CN114613926A (en) Based on Ce3+Doped CsPbCl3Quantum dot electroluminescent device and preparation method thereof
Lin et al. The relationship between basic group resonance and quantum yield of high efficiency red light fluorescent solutions
CN110416420A (en) Light emitting diode with quantum dots and preparation method thereof
CN101593815B (en) White organic electroluminescent device based on organic and inorganic composite color conversion membrane
CN113903867A (en) Electroluminescent LED and preparation method thereof
CN112968137A (en) Perovskite light-emitting diode and preparation method thereof
CN110224075B (en) Organic light-emitting diode and preparation method thereof
CN110224083B (en) Organic light-emitting diode and preparation method thereof

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE