WO2019091357A1 - Method for preparing mixed perovskite thin film and use thereof in led - Google Patents

Method for preparing mixed perovskite thin film and use thereof in led Download PDF

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WO2019091357A1
WO2019091357A1 PCT/CN2018/114031 CN2018114031W WO2019091357A1 WO 2019091357 A1 WO2019091357 A1 WO 2019091357A1 CN 2018114031 W CN2018114031 W CN 2018114031W WO 2019091357 A1 WO2019091357 A1 WO 2019091357A1
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layer
film
cspbbr
perovskite
led
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魏展画
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华侨大学
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds

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  • the invention relates to the field of optoelectronic technology, in particular to a preparation method of a mixed perovskite film and its application to LED.
  • Perovskite material is a new type of semiconductor material that has emerged in recent years. Its biggest feature is the simple preparation process. It can produce high-quality semiconductor film by solution method, which is significant compared with traditional high temperature, high voltage and complex semiconductor preparation processes. Technical advantage. Perovskite materials have very good photovoltaic properties, such as adjustable band gap, high visible light extinction coefficient, long carrier migration distance and few internal exciton composite defects, which makes it very suitable for the preparation of solar cells. Since 2012, through the unremitting efforts of scientists all over the world, the highest photoelectric conversion efficiency of perovskite solar cells has reached 22.1%, which is comparable to traditional silicon-based solar cells.
  • perovskite solar cells Compared with silicon-based solar cells, perovskite solar cells have lower manufacturing costs, lower production equipment requirements, and lower energy consumption and pollution. Therefore, perovskite solar cells are generally considered to be the most promising industrialization and lead new The high-tech cutting-edge technology of the round of photovoltaic revolution.
  • perovskite LEDs are expected to enter daily life and have a place in display and lighting.
  • the present invention provides a method for preparing a hybrid perovskite film and its use in LEDs, which overcomes the deficiencies of the prior art.
  • a method for preparing a mixed perovskite film which comprises dissolving CsPbBr 3 and CH 3 NH 3 Br in a DMSO solution, uniformly mixing and then forming a film having a thickness of 100-200 nm by spin coating; wherein the CsPbBr 3
  • the ratio to CH 3 NH 3 Br is 1:0.2-1.2, wherein the mass-mass solubility of CsPbBr 3 is 0.4-0.6M.
  • the ratio of the CsPbBr 3 and CH 3 NH 3 Br is 1:1.
  • a mixed perovskite film produced by the above-described preparation method the film having a CsPbBr 3 layer formed in situ and a CH 3 NH 3 Br layer attached to the surface of the CsPbBr 3 layer.
  • a green light perovskite LED comprising an anode, a hole transport layer, an electroluminescent layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked, wherein the electroluminescent layer is the above mixed perovskite film.
  • a passivation layer is disposed, the passivation layer being disposed between the electroluminescent layer and the electron injection layer.
  • the passivation layer is PMMA, SiO 2 or PVA and has a thickness of 2-10 nm.
  • the hole transport layer is one of PEDOT:PSS, PVK, PolyTPD, NiO x and has a thickness of 20-50 nm.
  • the electron transport layer is one of B3PYMPM, TPBi, SnO 2 , and ZnO.
  • the above method for preparing a green-light perovskite LED is to form a hole transport layer on an anode, and a mixed perovskite film is formed on the hole transport layer as an electroluminescent layer by the above method to form an electron transport on the electroluminescent layer.
  • the layer sequentially forms an electron injecting layer and a cathode on the electron transport layer.
  • the method further includes the step of forming a passivation layer on the surface of the electroluminescent layer, the electron transport layer being formed on the surface of the passivation layer.
  • the present invention has the following beneficial effects:
  • the mixed perovskite film of CsPbBr 3 and CH 3 NH 3 Br is obtained by solution method, which has high fluorescence intensity, large brightness, smooth surface without holes and good quality; the preparation process is simple, and can be realized at room temperature, suitable for Promote the application.
  • the perovskite LED device assembled by the hybrid perovskite film of the invention has excellent performance, the current efficiency can reach up to 77.18, the highest brightness exceeds 50,000 cd m -2 , and the highest external quantum efficiency is 20.31%, greatly Beyond the record of the prior art, it has promoted the development of perovskite LEDs, made industrialization for the future, and made great contributions to thousands of households.
  • Figure 1 is a schematic view of the process of Embodiment 1;
  • Example 2 is a backscattered electron imaging image of the mixed perovskite film of Example 1;
  • Figure 3 is a diagram showing the physical luminescence of CsPbBr 3 , MAPbBr 3 and the mixed perovskite film of Example 1 under ultraviolet light;
  • Figure 5 is a scanning electron micrograph of a mixed perovskite film of CsPbBr 3 , MAPbBr 3 and Example 1;
  • Figure 6 is a diagram showing the structure of an LED device of Embodiment 2.
  • Figure 7 is a physical diagram of the hybrid perovskite LED device of Example 2.
  • Figure 10 is a diagram showing the structure of an LED device of Embodiment 3.
  • Figure 11 is a current-voltage curve of pure electron and pure hole devices of a hybrid perovskite LED with or without a PMMA passivation layer;
  • Figure 12 is a graph of current efficiency of the device after the PMMA-free layer and the PMMA layer;
  • Figure 13 is a current-luminance-voltage graph of the hybrid perovskite LED device of Example 3.
  • 15 is a graph showing the current efficiency of different ratios of hybrid perovskite LED devices of Example 4.
  • CsPbBr 3 and CH 3 NH 3 Br are abbreviated as (MABr) dissolved in a DMSO solution having a molar ratio of CsPbBr 3 and MABr of 1:1 (abbreviated as Mixture-1.0), wherein CsPbBr 3 is The mass has a solubility of 0.5 M, and after mixing uniformly, a mixed perovskite film having a thickness of about 200 nm is formed by spin coating.
  • CsPbBr 3 precipitated first, and then precipitated on MABr and covered well on CsPbBr 3 film, thereby synthesizing the composite film structure of CsPbBr 3 layer and MABr layer in situ.
  • Pb in CsPbBr 3 is a heavy element, it appears brighter in backscatter imaging.
  • MABr is a light element, which is darker in backscatter imaging. After comparison, a layer of MABr of about 30 nm can be clearly seen. Covered on the CsPbBr 3 film, its performance is enhanced by the protection of the MABr layer.
  • the prepared mixed perovskite film (Mixture-1.0) was compared with a conventional CsPbBr 3 , CH 3 NH 3 PbBr 3 (abbreviated as MAPbBr 3 ) film:
  • Figure 3 shows three different perovskites under UV light.
  • the luminescence of the film, from left to right, is the CsPbBr 3 , MAPbBr 3 single perovskite film and the mixed perovskite film of the present embodiment, and it can be clearly seen that the mixed perovskite film emits high intensity green light, and CsPbBr 3 and MAPbBr 3 hardly emit light, and it can be seen that this embodiment produces a high-brightness perovskite film.
  • Figure 4 shows the fluorescence spectra of the above three perovskite films. It can be seen from the figure that the fluorescence of the CsPbBr 3 and MAPbBr 3 perovskite films is very weak, and the corresponding main peaks of luminescence are 526 nm and 538 nm, respectively. In contrast, the hybrid perovskite film has a very strong fluorescence, and the corresponding main peak of luminescence is 528 nm, which is close to that of pure CsPbBr 3 .
  • Figure 5 shows a scanning electron micrograph of the above three perovskite films, which shows the surface topography.
  • the CsPbBr 3 film is composed of particles of several hundred nanometers in size, and there are some holes between the particles and the particles.
  • the MAPbBr 3 film is composed of particles of several tens of nanometers, and some holes are also present on the surface. Since these holes cause leakage of the device in the LED device and cause a short circuit, the presence of these holes is very disadvantageous for the assembly of the LED device.
  • the mixed perovskite film is composed of micron-sized particles, and the particles are densely packed, and no obvious pores are found. In summary, considering that the mixed perovskite film can emit high-intensity green fluorescence and the surface of the film is flat without holes, it is very suitable for assembling perovskite LED devices.
  • a perovskite LED device structure includes an ITO anode, a PEDOT:PSS hole transport layer, a mixed perovskite thin film electroluminescent layer of Example 1, a B3PYMPM electron transport layer, and a LiF stacked in this order from bottom to top. Electron injection layer and Al cathode.
  • the method comprises the following steps: spin-coating on a ITO conductive glass to form a PEDOT:PSS layer, and spin-coating on the hole transport layer by the method of Example 1 to form a mixed perovskite film, which is sequentially processed on the mixed perovskite film by a conventional method.
  • a B3PYMPM layer, a LiF layer, and an Al cathode are formed. Conventional CsPbBr 3 and MAPbBr 3 films were assembled as electroluminescent layers as corresponding electroluminescent layers for comparison.
  • Fig. 7 is a view showing the device of the LED of the embodiment. It can be seen that the perovskite LED of the embodiment emits a very uniform and soft green light, and at the same time, by electrode customization technology, we can also make with "Pero- LED "logo” LED device.
  • Figure 8 shows the luminescence spectra of three perovskite LEDs (normalized). It can be seen from the figure that LED devices made of three perovskite materials can emit green at wavelengths between 522 and 530 nm. Light, in which the CsPbBr 3 and the mixed perovskite thin film device have a narrow half-width of the illuminating peak, that is, the chromaticity of the emitted light is pure and vivid.
  • Figure 9 shows a comparison of the current efficiencies of three perovskite LEDs.
  • Current efficiency is the ratio of luminescence intensity to injection current and can be used to evaluate the performance of LED devices. It can be seen from the figure that CsPbBr 3 and MAPbBr 3 calcium are used.
  • the performance of LED devices made from titanium oxide films is very poor, with current efficiencies of only 0.36 and 0.05.
  • LED devices made of hybrid perovskite films have shown excellent performance with a maximum current efficiency of 22.81, which is several hundred times higher than the previous two devices.
  • PVK, NiO x , PolyTPD or the like is used as the hole transport layer
  • TPBi, ZnO, SnO 2 or the like is used as the electron transport layer, and similar effects can be achieved.
  • the difference from Embodiment 2 is that the perovskite LED device of the present embodiment further includes a PMMA passivation layer interposed between the mixed perovskite thin film electroluminescent layer and the B3PYMPM electron transport layer, the thickness thereof. It is 2-10 nm.
  • the PMMA layer is used to reduce leakage inside the device.
  • Figure 11 shows the current-voltage curves of pure electronic and pure hole devices for a mixture of perovskite LEDs with or without a PMMA passivation layer. Assembly and testing of pure electron and pure hole devices is used to evaluate the electrons injected into the device. And an effective method of the number of holes. It can be seen from the figure that before the PMMA passivation layer is added, the number of injected electrons is larger than that of the injected holes, and the mismatched injection speed causes the device to leak. After the addition of the PMMA passivation layer, the number of injected electrons and holes is significantly reduced, and the number of both sides is basically equal, indicating that the electron hole injection efficiency at this time is balanced, which is beneficial to improve device performance.
  • Figure 12 shows the current efficiency statistics of the device without the PMMA layer and with the PMMA layer. From the figure, we can see that the device performance is greatly improved after the PMMA passivation layer is added.
  • Fig. 13 is a graph showing the current-luminance-voltage curve of the perovskite LED device of the present embodiment. It can be seen that the driving current of the device is small, but the luminance of the light is high, and the maximum luminance exceeds 10,000 cd m -2 .
  • Figure 14 shows the corresponding external quantum efficiency-luminescence intensity-voltage curve. It can be seen that the highest external quantum efficiency is 20.31% and the corresponding luminescence intensity is 3,400 cd m -2 . To the best of our knowledge, 20.31% of external quantum efficiency is a new world record, greatly surpassing previous work.
  • the molar ratios of CsPbBr 3 and MABr in the preparation of the mixed perovskite film were 1:0.4, 1:0.8, 1:1.0, and 1:1.2, respectively, and the mixed calcium and titanium of different ratios were detected.
  • the current efficiency of the mine LED device referring to Fig. 15, can be seen that the performance of the mine LED device is greatly improved compared with the prior art, and the performance of the ratio of 1.0 is optimal.

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Abstract

Disclosed in the present invention is a method for preparing a mixed perovskite thin film, comprising: dissolving CsPbBr3 and CH3NH3Br in a DMSO solution, mixing uniformly, and then forming a thin film with a thickness of 100-200 nm by spin coating. The ratio of CsPbBr3 to CH3NH3Br is 1: 0.2-1.2, and the solubility by mole of CsPbBr3 is 0.4-0.6 M. LED devices assembled with the prepared mixed perovskite thin film has excellent performance with current efficiency up to 77.18, the maximum brightness over 50,000 cdm-2, and the maximum external quantum efficiency of 20.31%, achieving significant improvements over the prior art.

Description

一种混合钙钛矿薄膜的制备方法及其于LED的应用Preparation method of mixed perovskite film and application thereof to LED 技术领域Technical field
本发明涉及光电技术领域，特别是涉及一种混合钙钛矿薄膜的制备方法及其于LED的应用。The invention relates to the field of optoelectronic technology, in particular to a preparation method of a mixed perovskite film and its application to LED.
背景技术Background technique
钙钛矿材料是近几年来兴起的新型半导体材料，其最大的特点就是制备工艺简单，可通过溶液法制得高质量的半导体薄膜，和传统高温、高压和复杂的半导体制备工艺相比，具有重大的技术优势。钙钛矿材料有非常优良的光伏特性，比如禁带宽度可调，可见光消光系数高，载流子迁移距离远和内部激子复合缺陷少等特点，这使得其非常适合用于制备太阳能电池。2012年至今，经过全世界科学家的不懈努力，钙钛矿太阳能电池的最高光电转换效率已经达到了22.1％，已经可以和传统的硅基太阳能电池媲美。和硅基太阳能电池相比，钙钛矿太阳能电池的制造成本更低，生产设备要求低，能耗和污染也少，因此钙钛矿太阳能电池被普遍认为是最有希望实现产业化并引领新的一轮光伏革命的高新尖技术。Perovskite material is a new type of semiconductor material that has emerged in recent years. Its biggest feature is the simple preparation process. It can produce high-quality semiconductor film by solution method, which is significant compared with traditional high temperature, high voltage and complex semiconductor preparation processes. Technical advantage. Perovskite materials have very good photovoltaic properties, such as adjustable band gap, high visible light extinction coefficient, long carrier migration distance and few internal exciton composite defects, which makes it very suitable for the preparation of solar cells. Since 2012, through the unremitting efforts of scientists all over the world, the highest photoelectric conversion efficiency of perovskite solar cells has reached 22.1%, which is comparable to traditional silicon-based solar cells. Compared with silicon-based solar cells, perovskite solar cells have lower manufacturing costs, lower production equipment requirements, and lower energy consumption and pollution. Therefore, perovskite solar cells are generally considered to be the most promising industrialization and lead new The high-tech cutting-edge technology of the round of photovoltaic revolution.
钙钛矿太阳能电池的相关研究已开展多年且取得了举世瞩目的成果，相较之下，钙钛矿LED的发展就逊色许多。究其原因，主要是因为缺少制备高质量和高亮度的钙钛矿薄膜的工艺，这就极大地限制了钙钛矿LED的器件性能。据调查，目前报道的钙钛矿LED的最高外量子转换效率仅为11％，这极大地落后于目前的OLED和无机LED，后两者都有高于25％的外量子转换效率。因此，钙钛矿LED想要在未来走进日常生活并在显示和照明领域占有一席之地的话，提高钙钛矿LED的外量子效率就变得非常迫切了。Related research on perovskite solar cells has been carried out for many years and has achieved remarkable results. In contrast, the development of perovskite LEDs is inferior. The reason is mainly due to the lack of a process for preparing high-quality and high-brightness perovskite films, which greatly limits the device performance of perovskite LEDs. According to the survey, the highest external quantum conversion efficiency of the currently reported perovskite LEDs is only 11%, which is greatly behind the current OLED and inorganic LEDs, both of which have external quantum conversion efficiencies higher than 25%. Therefore, it is very urgent to improve the external quantum efficiency of perovskite LEDs when perovskite LEDs are expected to enter daily life and have a place in display and lighting.
发明内容Summary of the invention
本发明提供了一种混合钙钛矿薄膜的制备方法及其于LED的应用，其克服了现有技术所存在的不足之处。The present invention provides a method for preparing a hybrid perovskite film and its use in LEDs, which overcomes the deficiencies of the prior art.
本发明解决其技术问题所采用的技术方案是：The technical solution adopted by the present invention to solve the technical problem thereof is:
一种混合钙钛矿薄膜的制备方法，所述方法是将CsPbBr 3和CH 3NH 3Br溶解于DMSO溶液中，混合均匀后通过旋涂形成厚度为100-200nm的薄膜；其中所述CsPbBr 3和CH 3NH 3Br的比例为1:0.2-1.2，其中CsPbBr 3的物质量溶度为0.4-0.6M。 A method for preparing a mixed perovskite film, which comprises dissolving CsPbBr 3 and CH 3 NH 3 Br in a DMSO solution, uniformly mixing and then forming a film having a thickness of 100-200 nm by spin coating; wherein the CsPbBr 3 The ratio to CH 3 NH 3 Br is 1:0.2-1.2, wherein the mass-mass solubility of CsPbBr 3 is 0.4-0.6M.
可选的，所述CsPbBr 3和CH 3NH 3Br的比例为1:1。 Optionally, the ratio of the CsPbBr 3 and CH 3 NH 3 Br is 1:1.
一种混合钙钛矿薄膜，所述薄膜通过上述制备方法制得，所述薄膜具有原位同步形成的CsPbBr 3层和附着于CsPbBr 3层表面的CH 3NH 3Br层。 A mixed perovskite film produced by the above-described preparation method, the film having a CsPbBr 3 layer formed in situ and a CH 3 NH 3 Br layer attached to the surface of the CsPbBr 3 layer.
一种绿光钙钛矿LED，包括依次层叠的阳极、空穴传输层、电致发光层、电子传输层、电子注入层和阴极，其中所述电致发光层为上述混合钙钛矿薄膜。A green light perovskite LED comprising an anode, a hole transport layer, an electroluminescent layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked, wherein the electroluminescent layer is the above mixed perovskite film.
可选的，还包括钝化层，所述钝化层设于所述电致发光层和电子注入层之间。Optionally, a passivation layer is disposed, the passivation layer being disposed between the electroluminescent layer and the electron injection layer.
可选的，所述钝化层为PMMA、SiO 2或PVA，厚度为2-10nm。 Optionally, the passivation layer is PMMA, SiO 2 or PVA and has a thickness of 2-10 nm.
可选的，所述空穴传输层是PEDOT：PSS、PVK、PolyTPD、NiO x中的一种，厚度为20-50nm。 Optionally, the hole transport layer is one of PEDOT:PSS, PVK, PolyTPD, NiO x and has a thickness of 20-50 nm.
可选的，所述电子传输层是B3PYMPM、TPBi、SnO 2、ZnO中的一种。 Optionally, the electron transport layer is one of B3PYMPM, TPBi, SnO 2 , and ZnO.
上述绿光钙钛矿LED的制备方法是于阳极上形成空穴传输层，通过上述方法于空穴传输层上形成混合钙钛矿薄膜作为电致发光层，于电致发光层上形成电子传输层，于电子传输层上依次形成电子注入层和阴极。The above method for preparing a green-light perovskite LED is to form a hole transport layer on an anode, and a mixed perovskite film is formed on the hole transport layer as an electroluminescent layer by the above method to form an electron transport on the electroluminescent layer. The layer sequentially forms an electron injecting layer and a cathode on the electron transport layer.
可选的，还包括于所述电致发光层表面形成钝化层的步骤，所述电子传输层形成于所述钝化层表面。Optionally, the method further includes the step of forming a passivation layer on the surface of the electroluminescent layer, the electron transport layer being formed on the surface of the passivation layer.
相较于现有技术，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、通过溶液法获得CsPbBr 3和CH 3NH 3Br的混合钙钛矿薄膜，其荧光强度高，亮度大，表面平整无孔洞，质量好；所用制备工艺简单，常温下即可实现，适于推广应用。 1. The mixed perovskite film of CsPbBr 3 and CH 3 NH 3 Br is obtained by solution method, which has high fluorescence intensity, large brightness, smooth surface without holes and good quality; the preparation process is simple, and can be realized at room temperature, suitable for Promote the application.
2、通过本发明的混合钙钛矿薄膜组装而成的钙钛矿LED器件性能优异，电流效率最高可达到77.18，最高亮度超过50,000cd m -2，最高的外量子效率是20.31％，极大地超越了现有技术的记录，推动了钙钛矿LED的发展，为其未来实现产业化，走进千家万户做出巨大的贡献。 2. The perovskite LED device assembled by the hybrid perovskite film of the invention has excellent performance, the current efficiency can reach up to 77.18, the highest brightness exceeds 50,000 cd m -2 , and the highest external quantum efficiency is 20.31%, greatly Beyond the record of the prior art, it has promoted the development of perovskite LEDs, made industrialization for the future, and made great contributions to thousands of households.
以下结合附图及实施例对本发明作进一步详细说明；但本发明的一种混合钙钛矿薄膜的制备方法及其于LED的应用不局限于实施例。The present invention will be further described in detail below with reference to the accompanying drawings and embodiments; however, the method for preparing a hybrid perovskite film of the present invention and its application to LEDs are not limited to the examples.
附图说明DRAWINGS
图1是实施例1的工艺示意图；Figure 1 is a schematic view of the process of Embodiment 1;
图2是实施例1的混合钙钛矿薄膜背散射电子成像图；2 is a backscattered electron imaging image of the mixed perovskite film of Example 1;
图3是紫外灯下CsPbBr 3、MAPbBr 3和实施例1的混合钙钛矿薄膜的实物发光情况图； Figure 3 is a diagram showing the physical luminescence of CsPbBr 3 , MAPbBr 3 and the mixed perovskite film of Example 1 under ultraviolet light;
图4是CsPbBr 3、MAPbBr 3和实施例1的混合钙钛矿薄膜的荧光光谱图； 4 is a fluorescence spectrum diagram of a mixed perovskite film of CsPbBr 3 , MAPbBr 3 and Example 1;
图5是CsPbBr 3、MAPbBr 3和实施例1的混合钙钛矿薄膜的扫描电镜图； Figure 5 is a scanning electron micrograph of a mixed perovskite film of CsPbBr 3 , MAPbBr 3 and Example 1;
图6是实施例2的LED器件结构；Figure 6 is a diagram showing the structure of an LED device of Embodiment 2;
图7是实施例2的混合钙钛矿LED器件实物图；Figure 7 is a physical diagram of the hybrid perovskite LED device of Example 2;
图8是CsPbBr 3LED器件、MAPbBr 3LED器件和实施例2的混合钙钛矿LED器件的发光光谱图； 8 is an illuminating spectrum of a CsPbBr 3 LED device, a MAPbBr 3 LED device, and a hybrid perovskite LED device of Example 2;
图9是CsPbBr 3LED器件、MAPbBr 3LED器件和实施例2的混合钙钛矿LED器件的电流效率比较图； 9 is a current efficiency comparison diagram of a CsPbBr 3 LED device, a MAPbBr 3 LED device, and a hybrid perovskite LED device of Example 2;
图10是实施例3的LED器件结构；Figure 10 is a diagram showing the structure of an LED device of Embodiment 3;
图11是有无PMMA钝化层的混合钙钛矿LED的纯电子和纯空穴器件的电流-电压曲线；Figure 11 is a current-voltage curve of pure electron and pure hole devices of a hybrid perovskite LED with or without a PMMA passivation layer;
图12是无PMMA层和有PMMA层后的器件电流效率统计图；Figure 12 is a graph of current efficiency of the device after the PMMA-free layer and the PMMA layer;
图13是实施例3的混合钙钛矿LED器件的电流-亮度-电压曲线图；Figure 13 is a current-luminance-voltage graph of the hybrid perovskite LED device of Example 3;
图14是实施例3的混合钙钛矿LED器件的外量子效率-发光强度-电压曲线；14 is an external quantum efficiency-luminous intensity-voltage curve of the hybrid perovskite LED device of Example 3;
图15是实施例4的不同配比的混合钙钛矿LED器件的电流效率统计图。15 is a graph showing the current efficiency of different ratios of hybrid perovskite LED devices of Example 4.
具体实施方式Detailed ways
实施例1Example 1
参考图1，将CsPbBr 3和CH 3NH 3Br简写为(MABr)溶解于DMSO溶液中，所述CsPbBr 3 和MABr的摩尔比为1:1(简写为Mixture-1.0)，其中CsPbBr 3的物质量溶度为0.5M，混合均匀后通过旋涂形成厚度约为200nm的混合钙钛矿薄膜。由于CsPbBr 3和MABr于DMSO溶液中溶解度的差异，使得CsPbBr 3先析出，MABr后析出并很好地覆盖在CsPbBr 3薄膜上，从而原位同步形成CsPbBr 3层和MABr层的复合膜结构。参考图2，因为CsPbBr 3中的Pb是重元素，在背散射成像中显得比较亮，MABr都是轻元素，背散射成像时显得比较暗，对比后可以清晰地看到一层30nm左右的MABr覆盖在CsPbBr 3薄膜上，通过MABr层的保护作用提高其性能。 Referring to Figure 1, CsPbBr 3 and CH 3 NH 3 Br are abbreviated as (MABr) dissolved in a DMSO solution having a molar ratio of CsPbBr 3 and MABr of 1:1 (abbreviated as Mixture-1.0), wherein CsPbBr 3 is The mass has a solubility of 0.5 M, and after mixing uniformly, a mixed perovskite film having a thickness of about 200 nm is formed by spin coating. Due to the difference in solubility of CsPbBr 3 and MABr in DMSO solution, CsPbBr 3 precipitated first, and then precipitated on MABr and covered well on CsPbBr 3 film, thereby synthesizing the composite film structure of CsPbBr 3 layer and MABr layer in situ. Referring to Figure 2, because Pb in CsPbBr 3 is a heavy element, it appears brighter in backscatter imaging. MABr is a light element, which is darker in backscatter imaging. After comparison, a layer of MABr of about 30 nm can be clearly seen. Covered on the CsPbBr 3 film, its performance is enhanced by the protection of the MABr layer.
将制得的混合钙钛矿薄膜(Mixture-1.0)与常规的CsPbBr 3、CH 3NH 3PbBr 3(简写为MAPbBr 3)薄膜进行比较：图3展示了紫外灯下三种不同的钙钛矿薄膜的发光情况，从左到右依次是CsPbBr 3、MAPbBr 3单一钙钛矿薄膜和本实施例的混合钙钛矿薄膜，可以明显地看出混合钙钛矿薄膜发出高强度的绿光，而CsPbBr 3和MAPbBr 3几乎不发光，可见本实施例制备出高亮度的钙钛矿薄膜。图4展示了上述三种钙钛矿薄膜的荧光光谱图，从图中可以看出CsPbBr 3和MAPbBr 3钙钛矿薄膜的荧光非常微弱，对应的发光主峰分别是526nm和538nm。相较之下，混合钙钛矿薄膜的荧光非常强，对应的发光主峰是528nm，和纯的CsPbBr 3的发光比较接近。图5展示了上述三种钙钛矿薄膜的扫描电镜图，也就是展示了其表面形貌。从图中可以看出，CsPbBr 3薄膜是由几百纳米大小的颗粒组成，颗粒与颗粒之间存在一些孔洞，MAPbBr 3薄膜是由几十纳米大小的颗粒组成，表面也存在一些孔洞。因为这些孔洞在LED器件中会造成器件漏电，严重的会造成短路，所以这些孔洞的存在是非常不利于LED器件的组装的。然而混合钙钛矿薄膜是由微米级颗粒组成，且颗粒堆积紧密，没有发现有明显的孔洞。综上，考虑到混合钙钛矿薄膜可以发出高强度的绿色荧光且膜表面平整无孔洞，非常适合于组装钙钛矿LED器件。 The prepared mixed perovskite film (Mixture-1.0) was compared with a conventional CsPbBr 3 , CH 3 NH 3 PbBr 3 (abbreviated as MAPbBr 3 ) film: Figure 3 shows three different perovskites under UV light. The luminescence of the film, from left to right, is the CsPbBr 3 , MAPbBr 3 single perovskite film and the mixed perovskite film of the present embodiment, and it can be clearly seen that the mixed perovskite film emits high intensity green light, and CsPbBr 3 and MAPbBr 3 hardly emit light, and it can be seen that this embodiment produces a high-brightness perovskite film. Figure 4 shows the fluorescence spectra of the above three perovskite films. It can be seen from the figure that the fluorescence of the CsPbBr 3 and MAPbBr 3 perovskite films is very weak, and the corresponding main peaks of luminescence are 526 nm and 538 nm, respectively. In contrast, the hybrid perovskite film has a very strong fluorescence, and the corresponding main peak of luminescence is 528 nm, which is close to that of pure CsPbBr 3 . Figure 5 shows a scanning electron micrograph of the above three perovskite films, which shows the surface topography. It can be seen from the figure that the CsPbBr 3 film is composed of particles of several hundred nanometers in size, and there are some holes between the particles and the particles. The MAPbBr 3 film is composed of particles of several tens of nanometers, and some holes are also present on the surface. Since these holes cause leakage of the device in the LED device and cause a short circuit, the presence of these holes is very disadvantageous for the assembly of the LED device. However, the mixed perovskite film is composed of micron-sized particles, and the particles are densely packed, and no obvious pores are found. In summary, considering that the mixed perovskite film can emit high-intensity green fluorescence and the surface of the film is flat without holes, it is very suitable for assembling perovskite LED devices.
实施例2Example 2
参考图6，一种钙钛矿LED器件结构包括由下至上依次层叠的ITO阳极、PEDOT：PSS空穴传输层、实施例1的混合钙钛矿薄膜电致发光层、B3PYMPM电子传输层、LiF电子注入层和Al阴极。其制作方法为：于ITO导电玻璃上旋涂形成PEDOT：PSS层，通过实施例1的方法于空穴传输层上旋涂形成混合钙钛矿薄膜，于混合钙钛矿薄膜上通过常 规方法依次形成B3PYMPM层、LiF层和Al阴极。将常规的CsPbBr 3和MAPbBr 3薄膜作为电致发光层组装相应LED器件作为对比。 Referring to FIG. 6, a perovskite LED device structure includes an ITO anode, a PEDOT:PSS hole transport layer, a mixed perovskite thin film electroluminescent layer of Example 1, a B3PYMPM electron transport layer, and a LiF stacked in this order from bottom to top. Electron injection layer and Al cathode. The method comprises the following steps: spin-coating on a ITO conductive glass to form a PEDOT:PSS layer, and spin-coating on the hole transport layer by the method of Example 1 to form a mixed perovskite film, which is sequentially processed on the mixed perovskite film by a conventional method. A B3PYMPM layer, a LiF layer, and an Al cathode are formed. Conventional CsPbBr 3 and MAPbBr 3 films were assembled as electroluminescent layers as corresponding electroluminescent layers for comparison.
图7展示了本实施例LED的器件实物图，可以看出本实施例的钙钛矿LED发出非常均匀和柔和的绿光，同时，通过电极定制技术，我们还可以做出带有“Pero-LED”logo的发光LED器件。图8展示了三种钙钛矿LED的发光光谱图(已归一化)，从图中可以看出三种钙钛矿材料做出的LED器件都能发出波长位于522-530nm之间的绿光，其中CsPbBr 3和混合钙钛矿薄膜器件的发光峰半峰宽较窄，也就是其发出的光色度纯且鲜艳。图9展示了三种钙钛矿LED的电流效率比较图，电流效率是发光强度和注入电流的比值，能用于评估了LED器件的性能，从图中可以看出用CsPbBr 3和MAPbBr 3钙钛矿薄膜做出的LED器件性能非常差，仅有0.36和0.05的电流效率。然而混合钙钛矿薄膜做成的LED器件表现出了优异的性能，最高的电流效率达到了22.81，比前两种器件高出了几百倍。 Fig. 7 is a view showing the device of the LED of the embodiment. It can be seen that the perovskite LED of the embodiment emits a very uniform and soft green light, and at the same time, by electrode customization technology, we can also make with "Pero- LED "logo" LED device. Figure 8 shows the luminescence spectra of three perovskite LEDs (normalized). It can be seen from the figure that LED devices made of three perovskite materials can emit green at wavelengths between 522 and 530 nm. Light, in which the CsPbBr 3 and the mixed perovskite thin film device have a narrow half-width of the illuminating peak, that is, the chromaticity of the emitted light is pure and vivid. Figure 9 shows a comparison of the current efficiencies of three perovskite LEDs. Current efficiency is the ratio of luminescence intensity to injection current and can be used to evaluate the performance of LED devices. It can be seen from the figure that CsPbBr 3 and MAPbBr 3 calcium are used. The performance of LED devices made from titanium oxide films is very poor, with current efficiencies of only 0.36 and 0.05. However, LED devices made of hybrid perovskite films have shown excellent performance with a maximum current efficiency of 22.81, which is several hundred times higher than the previous two devices.
此外，本领域技术人员应知，以PVK、NiO x、PolyTPD等作为空穴传输层，以TPBi、ZnO、SnO 2等作为电子传输层，可以实现相近的效果。 Further, it is known to those skilled in the art that PVK, NiO x , PolyTPD or the like is used as the hole transport layer, and TPBi, ZnO, SnO 2 or the like is used as the electron transport layer, and similar effects can be achieved.
实施例3Example 3
参考图10，与实施例2的差别在于，本实施例的钙钛矿LED器件还包括夹设于混合钙钛矿薄膜电致发光层和B3PYMPM电子传输层之间的PMMA钝化层，其厚度为2-10nm。PMMA层是用于减少器件内部的漏电情况。Referring to FIG. 10, the difference from Embodiment 2 is that the perovskite LED device of the present embodiment further includes a PMMA passivation layer interposed between the mixed perovskite thin film electroluminescent layer and the B3PYMPM electron transport layer, the thickness thereof. It is 2-10 nm. The PMMA layer is used to reduce leakage inside the device.
图11展示了有无PMMA钝化层的混合物钙钛矿LED的纯电子和纯空穴器件的电流-电压曲线，组装和测试纯电子和纯空穴器件是用于评估注入到器件中的电子和空穴数量的有效方法。从图中可以看出，在未加PMMA钝化层之前，注入电子的数量多于注入的空穴，这不匹配的注入速度也就造成了器件漏电。加入PMMA钝化层后，注入电子和空穴的数量都有明显的下降，且双方的数量基本相当，说明此时的电子空穴注入效率达到了平衡，这是有利于提高器件性能的。图12展示了无PMMA层和有PMMA层后的器件电流效率统计图，从图中我们可以发现，加入PMMA钝化层后，器件性能得到了极大的提升。Figure 11 shows the current-voltage curves of pure electronic and pure hole devices for a mixture of perovskite LEDs with or without a PMMA passivation layer. Assembly and testing of pure electron and pure hole devices is used to evaluate the electrons injected into the device. And an effective method of the number of holes. It can be seen from the figure that before the PMMA passivation layer is added, the number of injected electrons is larger than that of the injected holes, and the mismatched injection speed causes the device to leak. After the addition of the PMMA passivation layer, the number of injected electrons and holes is significantly reduced, and the number of both sides is basically equal, indicating that the electron hole injection efficiency at this time is balanced, which is beneficial to improve device performance. Figure 12 shows the current efficiency statistics of the device without the PMMA layer and with the PMMA layer. From the figure, we can see that the device performance is greatly improved after the PMMA passivation layer is added.
图13展示了本实施例钙钛矿LED器件的电流-亮度-电压曲线图，可见器件的驱动电流很小，但是发光亮度很高，最高亮度超过10,000cd m -2。图14展示了对应的外量子效 率-发光强度-电压曲线，可以看出最高的外量子效率是20.31％，相应的发光强度是3,400cd m -2。据我们所知，20.31％的外量子效率是新的世界纪录，极大地超越了之前的工作。 Fig. 13 is a graph showing the current-luminance-voltage curve of the perovskite LED device of the present embodiment. It can be seen that the driving current of the device is small, but the luminance of the light is high, and the maximum luminance exceeds 10,000 cd m -2 . Figure 14 shows the corresponding external quantum efficiency-luminescence intensity-voltage curve. It can be seen that the highest external quantum efficiency is 20.31% and the corresponding luminescence intensity is 3,400 cd m -2 . To the best of our knowledge, 20.31% of external quantum efficiency is a new world record, greatly surpassing previous work.
此外，本领域技术人员应知，以SiO 2或PVA作为钝化层，可以实现相近的效果。 Further, it will be apparent to those skilled in the art that similar effects can be achieved with SiO 2 or PVA as the passivation layer.
实施例4Example 4
参考实施例3的LED器件结构，调整混合钙钛矿薄膜制备中CsPbBr 3和MABr的摩尔比分别为1：0.4、1：0.8、1：1.0和1：1.2，检测不同配比的混合钙钛矿LED器件的电流效率，参考图15，可见相对现有技术，其性能均得到了很大的提升，其中配比为1.0的性能最佳。 Referring to the LED device structure of Example 3, the molar ratios of CsPbBr 3 and MABr in the preparation of the mixed perovskite film were 1:0.4, 1:0.8, 1:1.0, and 1:1.2, respectively, and the mixed calcium and titanium of different ratios were detected. The current efficiency of the mine LED device, referring to Fig. 15, can be seen that the performance of the mine LED device is greatly improved compared with the prior art, and the performance of the ratio of 1.0 is optimal.
上述实施例仅用来进一步说明本发明的一种混合钙钛矿薄膜的制备方法及其于LED的应用，但本发明并不局限于实施例，凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均落入本发明技术方案的保护范围内。The above embodiments are only used to further illustrate a method for preparing a hybrid perovskite film of the present invention and its application to LEDs, but the present invention is not limited to the embodiments, and the above embodiments are made in accordance with the technical essence of the present invention. Any simple modifications, equivalent changes, and modifications are intended to fall within the scope of the present invention.

Claims (14)

  1. 一种混合钙钛矿薄膜的制备方法，其特征在于：将CsPbBr 3和CH 3NH 3Br溶解于DMSO溶液中，混合均匀后通过旋涂形成厚度为100-200nm的薄膜；其中所述CsPbBr 3和CH 3NH 3Br的比例为1:0.2-1.2，其中CsPbBr 3的物质量溶度为0.4-0.6M。 A method for preparing a mixed perovskite film, characterized in that CsPbBr 3 and CH 3 NH 3 Br are dissolved in a DMSO solution, uniformly mixed, and then formed into a film having a thickness of 100-200 nm by spin coating; wherein the CsPbBr 3 The ratio to CH 3 NH 3 Br is 1:0.2-1.2, wherein the mass-mass solubility of CsPbBr 3 is 0.4-0.6M.
  2. 根据权利要求1所述的制备方法，其特征在于：所述CsPbBr 3和CH 3NH 3Br的比例为1:1。 The preparation method according to claim 1, wherein the ratio of the CsPbBr 3 and the CH 3 NH 3 Br is 1:1.
  3. 一种混合钙钛矿薄膜，其特征在于：所述薄膜通过权利要求1～2任一项所述的制备方法制得，所述薄膜具有原位同步形成的CsPbBr 3层和附着于CsPbBr 3层表面的CH 3NH 3Br层。 A mixed perovskite film, characterized in that the film is obtained by the preparation method according to any one of claims 1 to 2, wherein the film has a CsPbBr 3 layer formed in situ and attached to a CsPbBr 3 layer The surface of the CH 3 NH 3 Br layer.
  4. 一种绿光钙钛矿LED，其特征在于：包括依次层叠的阳极、空穴传输层、电致发光层、电子传输层、电子注入层和阴极，其中所述电致发光层为权利要求3所述的混合钙钛矿薄膜。A green light perovskite LED comprising: an anode, a hole transport layer, an electroluminescent layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked, wherein the electroluminescent layer is according to claim 3 The mixed perovskite film.
  5. 根据权利要求4所述的绿光钙钛矿LED，其特征在于：还包括钝化层，所述钝化层设于所述电致发光层和电子注入层之间。The green light perovskite LED according to claim 4, further comprising a passivation layer disposed between the electroluminescent layer and the electron injecting layer.
  6. 根据权利要求5所述的绿光钙钛矿LED，其特征在于：所述钝化层为PMMA、SiO 2或PVA，厚度为2-10nm。 The green light perovskite LED according to claim 5, wherein the passivation layer is PMMA, SiO 2 or PVA and has a thickness of 2 to 10 nm.
  7. 根据权利要求4所述的绿光钙钛矿LED，其特征在于：所述空穴传输层是PEDOT：PSS、PVK、PolyTPD、NiO x中的一种，厚度为20-50nm。 Claim green LED 4 of the perovskite, wherein: the hole transport layer is PEDOT: PSS, PVK, PolyTPD, one kind of NiO x, a thickness of 20-50nm.
  8. 根据权利要求4所述的绿光钙钛矿LED，其特征在于：所述电子传输层是B3PYMPM、TPBi、SnO 2、ZnO中的一种。 The green light perovskite LED according to claim 4, wherein the electron transport layer is one of B3PYMPM, TPBi, SnO 2 , and ZnO.
  9. 权利要求4～8任一项所述绿光钙钛矿LED的制备方法，其特征在于：于阳极上形成空穴传输层，通过权利要求1～2任一项所述方法于空穴传输层上形成混合钙钛矿薄膜作为电致发光层，于电致发光层上形成电子传输层，于电子传输 层上依次形成电子注入层和阴极。The method for producing a green light perovskite LED according to any one of claims 4 to 8, wherein a hole transport layer is formed on the anode, and the hole transport layer is formed by the method according to any one of claims 1 to 2. A mixed perovskite film is formed as an electroluminescent layer, an electron transport layer is formed on the electroluminescent layer, and an electron injecting layer and a cathode are sequentially formed on the electron transporting layer.
  10. 根据权利要求9所述的制备方法，其特征在于：还包括于所述电致发光层表面形成钝化层的步骤，所述电子传输层形成于所述钝化层表面。The method according to claim 9, further comprising the step of forming a passivation layer on the surface of the electroluminescent layer, the electron transport layer being formed on a surface of the passivation layer.
  11. 一种混合钙钛矿薄膜，其特征在于：其成膜物质包括CsPbBr 3和CH 3NH 3Br，并且厚度为100-200nm的薄膜；其中所述CsPbBr 3和CH 3NH 3Br的比例为1:0.2-1.2。 A mixed perovskite film characterized in that the film-forming substance comprises CsPbBr 3 and CH 3 NH 3 Br, and a film having a thickness of 100-200 nm; wherein the ratio of the CsPbBr 3 and CH 3 NH 3 Br is 1 : 0.2-1.2.
  12. 根据权利要求11所述的制备方法，其特征在于：所述CsPbBr 3和CH 3NH 3Br的比例为1:1。 The production method according to claim 11, wherein the ratio of the CsPbBr 3 and the CH 3 NH 3 Br is 1:1.
  13. 一种混合钙钛矿薄膜，其特征在于：所述薄膜通过权利要求11～12任一项所述的薄膜，所述薄膜具有原位同步形成的CsPbBr 3层和附着于CsPbBr 3层表面的CH 3NH 3Br层。 A mixed perovskite film, characterized in that the film comprises the film according to any one of claims 11 to 12, which has a CsPbBr 3 layer formed in situ and a CH attached to the surface of the CsPbBr 3 layer. 3 NH 3 Br layer.
  14. 一种绿光钙钛矿LED，其特征在于：包括依次层叠的阳极、空穴传输层、电致发光层、电子传输层、电子注入层和阴极，其中所述电致发光层为权利要求11或13所述的混合钙钛矿薄膜。A green light perovskite LED comprising: an anode, a hole transport layer, an electroluminescent layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked, wherein the electroluminescent layer is according to claim 11 Or a mixed perovskite film as described in 13.
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