CN111785846A - A green perovskite light-emitting diode based on surface post-treatment process and its preparation - Google Patents
A green perovskite light-emitting diode based on surface post-treatment process and its preparation Download PDFInfo
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Abstract
一种基于表面后处理工艺的绿光钙钛矿发光二极管及制备,属于半导体固体发光器件领域,具体涉及以丁基溴化胺作为钙钛矿发光层的表面钝化层,用于钙钛矿发光二极管。其结构包括透明导电基底、空穴传输层、钙钛矿层、电子传输层、电极修饰层、金属铝电极。主要以旋涂的方法将丁基溴化胺修饰在钙钛矿发光层之上。该表面钝化层通过诱导钙钛矿重结晶过程,提高钙钛矿层的致密性,钝化其表面缺陷,有效降低膜内非辐射复合所占的比例。通过该工艺集成的全无机绿光钙钛矿发光二极管的启动电压显著降低,发光亮度和发光效率得到大幅提升,稳定性明显改善。A green light perovskite light-emitting diode based on a surface post-treatment process and preparation thereof belong to the field of semiconductor solid light-emitting devices, in particular to the use of butylamine bromide as a surface passivation layer of a perovskite light-emitting layer, which is used for perovskite led. Its structure includes a transparent conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer, an electrode modification layer, and a metal aluminum electrode. The butylamine bromide is mainly modified on the perovskite light-emitting layer by spin coating. The surface passivation layer improves the compactness of the perovskite layer by inducing the recrystallization process of the perovskite, passivates its surface defects, and effectively reduces the proportion of non-radiative recombination in the film. The start-up voltage of the all-inorganic green perovskite light-emitting diode integrated through this process is significantly reduced, the luminous brightness and luminous efficiency are greatly improved, and the stability is significantly improved.
Description
技术领域technical field
本发明属于钙钛矿发光二极管领域,具体涉及以绿光钙钛矿发光二极管为主体,在钙钛矿发光层表面旋涂丁基溴化胺作为表面钝化层与其在半导体发光器件中的应用。The invention belongs to the field of perovskite light emitting diodes, and particularly relates to a green light perovskite light emitting diode as the main body, spin-coating butylamine bromide on the surface of the perovskite light emitting layer as a surface passivation layer and its application in semiconductor light emitting devices.
技术背景technical background
发光二极管(LED)凭借其节能省电、环境友好、体积小、响应快、寿命长等优点,在指示、显示、背光源、普通照明等领域获得了广泛应用,尤其在节能省电问题上,LED是目前取代白炽灯泡的最佳选择。LED器件中的常用的半导体发光材料有无机发光材料、有机发光材料和量子点发光材料等。传统的无机发光材料存在色纯度低且需要高能耗的真空沉积制备工艺等缺点。可溶液加工的有机发光二极管(OLED)和量子点发光二极管(QLED) 虽具有较好的发光性能,但是目前正在经历或者刚开始商业化进程,存在蓝光OLED寿命短、QLED中铬的毒性高、产率低以及成本高等缺点需要克服。金属卤化物钙铁矿材料作为一种可通过低温溶液工艺制备的直接带隙半导体材料,具有连续可调的发光波长、高发光色纯度等特点,被认为是下一代LED器件的有力竞争者。Light-emitting diodes (LEDs) have been widely used in indication, display, backlight, general lighting and other fields due to their advantages of energy saving, environmental friendliness, small size, fast response, and long life, especially in the issue of energy saving and power saving. LEDs are currently the best option to replace incandescent light bulbs. Commonly used semiconductor light-emitting materials in LED devices include inorganic light-emitting materials, organic light-emitting materials and quantum dot light-emitting materials. Traditional inorganic light-emitting materials have disadvantages such as low color purity and high energy-consuming vacuum deposition preparation process. Although solution-processable organic light-emitting diodes (OLEDs) and quantum dot light-emitting diodes (QLEDs) have good luminescent properties, they are currently undergoing or have just begun commercialization, including the short lifespan of blue OLEDs, the high toxicity of chromium in QLEDs, The disadvantages of low yield and high cost need to be overcome. As a direct bandgap semiconductor material that can be prepared by low temperature solution process, metal halide perovskite material has the characteristics of continuously tunable emission wavelength and high emission color purity, and is considered as a strong competitor for next-generation LED devices.
用于制作LED的钙钛矿材料的结构为ABX3,其中A=CH3NH3 +(MA),CH3(NH2)2 +(FA),Cs+;B=Pb2+,Sn2+;X=Cl-,Br-,I-。基于钙钛矿材料的发光二极管(PeLED)目前的功率转换效率已经超过20%,尽管发展迅速,但是目前PeLED器件仍旧存在诸多基础问题,无论是钙钛矿材料作为发光层本身所存在的问题,还是将它结合在器件中时所引入的各界面之间的问题,或者是器件工作的时候存在的问题,都是亟需研究者去解决的。其中,钙钛矿发光层的形貌质量直接决定了PeLED器件的效率和稳定性,但是目前通过溶液法制备的钙钛矿薄膜往往具有较高的缺陷态密度。因此,开发一种既能改善钙钛矿层的形貌质量又能有效钝化钙钛矿层缺陷态以及平衡电子和空穴注入的表面后处理工艺对于制作高效稳定的钙钛矿发光二极管具有重要意义。The structure of the perovskite material used to make the LED is ABX 3 , wherein A=CH 3 NH 3 + (MA), CH 3 (NH 2 ) 2 + (FA), Cs + ; B=Pb 2+ , Sn 2 + ; X=Cl - , Br - , I - . The current power conversion efficiency of light-emitting diodes (PeLEDs) based on perovskite materials has exceeded 20%. Despite the rapid development, there are still many basic problems in PeLED devices. The problems between the interfaces introduced when it is combined in the device, or the problems existing when the device works, are urgently needed by researchers to solve. Among them, the morphology quality of the perovskite light-emitting layer directly determines the efficiency and stability of the PeLED device, but the perovskite films prepared by the solution method usually have a high density of defect states. Therefore, developing a surface post-treatment process that can not only improve the morphology quality of the perovskite layer, but also effectively passivate the defect states of the perovskite layer and balance the injection of electrons and holes is of great significance for the fabrication of efficient and stable perovskite light-emitting diodes. .
发明内容SUMMARY OF THE INVENTION
为了解决现有技术的问题,本发明的目的之一是提供一种表面后处理工艺。In order to solve the problems of the prior art, one of the objects of the present invention is to provide a surface post-treatment process.
本发明的目的之二是提供一种绿光钙钛矿发光二极管,该LED器件集成过程包括上述表面后处理工艺。Another object of the present invention is to provide a green perovskite light-emitting diode, and the LED device integration process includes the above-mentioned surface post-treatment process.
发明人研究发现,丁基溴化胺作为表面钝化层复合到绿光钙钛矿发光二极管的钙钛矿发光层之上,可以诱导钙钛矿重结晶过程,降低薄膜表面针孔数量,提高致密性,钝化钙钛矿晶界和表面的缺陷态,提高有效的辐射复合所占的比例,平衡电子和空穴注入到钙钛矿层的速率。制作的LED具有启动电压低、发光亮度和发光效率高、稳定性好等优点。本发明制作工艺简单、成本低廉、重复性好、适合制作大面积的发光二极管。The inventor's research found that butylamine bromide as a surface passivation layer compounded on the perovskite light-emitting layer of the green perovskite light-emitting diode can induce the perovskite recrystallization process, reduce the number of pinholes on the surface of the film, and improve the Density, passivation of perovskite grain boundaries and defect states on the surface, increasing the proportion of effective radiative recombination, and balancing the rate of electron and hole injection into the perovskite layer. The produced LED has the advantages of low starting voltage, high luminous brightness and luminous efficiency, and good stability. The invention has the advantages of simple manufacturing process, low cost and good repeatability, and is suitable for manufacturing large-area light emitting diodes.
本发明是通过以下技术手段实现的:The present invention is achieved by the following technical means:
一种基于表面后处理工艺的绿光钙钛矿发光二极管,其特征在于,器件结构包括依次层叠的ITO透明导电基底/空穴传输层/(钙钛矿层+表面钝化层)/电子传输层/电极修饰层/铝电极。A green light perovskite light-emitting diode based on surface post-treatment process, characterized in that the device structure comprises an ITO transparent conductive substrate/hole transport layer/(perovskite layer+surface passivation layer)/electron transport layer stacked in sequence / electrode modification layer / aluminum electrode.
所述的导电基底为ITO导电玻璃;The conductive substrate is ITO conductive glass;
所述的空穴传输层的材料为TFB、PEDOT:PSS、CBP、PVK中的任意一种半导体材料;The material of the hole transport layer is any semiconductor material in TFB, PEDOT:PSS, CBP, PVK;
所述的电子传输层的材料为TPBi、F8、BCP、PCBM中的任意一种半导体材料。The material of the electron transport layer is any semiconductor material among TPBi, F8, BCP, and PCBM.
所述的钙钛矿发光层其化学通式为APbBr3,其中A为铯、甲胺、甲脒阳离子中的一种或多种不同比例的混合阳离子。The general chemical formula of the perovskite light-emitting layer is APbBr 3 , wherein A is one or more mixed cations in different proportions among cesium, methylamine, and formamidine cations.
所述的钙钛矿层+表面钝化层指的是在钙钛矿层上复合有表面钝化层。The perovskite layer+surface passivation layer refers to that the perovskite layer is compounded with a surface passivation layer.
电极修饰层为氟化锂(LiF)。The electrode modification layer is lithium fluoride (LiF).
上述所述的一种基于表面后处理工艺的绿光钙钛矿发光二极管的方法,其特征在于,包括以下步骤:The above-mentioned method for a green perovskite light-emitting diode based on a surface post-treatment process is characterized in that, comprising the following steps:
1)空穴传输层的制备:1) Preparation of hole transport layer:
空穴传输层的制备方法:将稀释好的空穴传输层分散液或溶液旋涂于洁净的ITO导电基底上,退火后形成一层致密的空穴传输层薄膜;The preparation method of the hole transport layer: spin-coating the diluted hole transport layer dispersion or solution on a clean ITO conductive substrate, and after annealing, a dense hole transport layer film is formed;
旋涂条件为3000~5000rpm,时间1min;退火条件为150℃,时间10~30min;Spin coating condition is 3000~5000rpm, time 1min; annealing condition is 150℃,
2)钙钛矿层+表面钝化层的制备:2) Preparation of perovskite layer + surface passivation layer:
按照化学通式APbBr3中的元素摩尔比进行配料,称取相应量的ABr、PbB2,溶于二甲基亚砜(DMSO)或N,N-二甲基甲酰胺(DMF)中的一种或两种的混合溶剂得到前驱体溶液;第一步先将前驱体溶液旋涂于步骤1)中的薄膜上,并进行退火;旋涂条件为1500~3000 rpm,时间2min;退火条件为80~120℃,时间10~20min;第二步在表面旋涂丁基溴化胺溶液,经退火后得到表面钝化的钙钛矿薄膜;旋涂条件为2000~4000rpm,时间30~60s;退火条件为80~100℃,时间5~10min。According to the element molar ratio in the chemical formula APbBr 3 , the corresponding amount of ABr and PbB 2 are weighed and dissolved in dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF). One or two mixed solvents are used to obtain the precursor solution; the first step is to spin-coat the precursor solution on the film in step 1) and anneal it; the spin coating conditions are 1500-3000 rpm, and the time is 2 min; the annealing conditions are 80~120℃,
进一步优选前驱体溶液的浓度为0.2~0.4M,丁基溴化胺溶液的浓度为1~9mg/mL。More preferably, the concentration of the precursor solution is 0.2 to 0.4 M, and the concentration of the butylamine bromide solution is 1 to 9 mg/mL.
3)电子传输层的制备:3) Preparation of electron transport layer:
电子传输层的制备方法:将电子传输层通过真空蒸镀沉积于步骤2)中的薄膜上,蒸发速率保持在之间,厚度为30~50nm。The preparation method of the electron transport layer: the electron transport layer is deposited on the thin film in step 2) by vacuum evaporation, and the evaporation rate is kept at In between, the thickness is 30 to 50 nm.
4)电极修饰层/铝电极的制备:4) Preparation of electrode modification layer/aluminum electrode:
电极修饰层/铝电极的制备方法:将电极修饰层和铝电极通过真空蒸镀依次沉积于步骤 3)中的薄膜上,蒸发速率分别为和厚度分别为1nm和60~100nm。The preparation method of the electrode modification layer/aluminum electrode: the electrode modification layer and the aluminum electrode are sequentially deposited on the film in step 3) by vacuum evaporation, and the evaporation rates are respectively and The thicknesses are 1 nm and 60-100 nm, respectively.
步骤3和4)的蒸镀过程中,蒸镀仓内的压力要小于3.7×10-6Torr,才可开始蒸镀,蒸发速率要保持稳定。During the evaporation process of steps 3 and 4), the pressure in the evaporation chamber must be less than 3.7×10 -6 Torr before evaporation can be started, and the evaporation rate must be kept stable.
步骤2)中的第一步溶液旋涂法为反溶剂一步成膜法,反溶剂滴加方法为旋涂后正数第 30~35s开始匀速滴加反溶剂,滴加时间为1~3s;反溶剂为氯苯、甲苯、乙酸乙酯、乙醚中的一种或几种的混合溶剂,滴加量为每4cm2面积滴加150~200μl。The first step solution spin coating method in step 2) is an anti-solvent one-step film-forming method, and the anti-solvent dropping method is that the anti-solvent is added dropwise at a constant speed at the positive 30-35 s after the spin coating, and the dropping time is 1-3 s; The anti-solvent is one or more mixed solvents of chlorobenzene, toluene, ethyl acetate and ether, and the dropwise addition amount is 150-200 μl per 4 cm 2 area.
一种基于表面后处理工艺的绿光钙钛矿发光二极管的方法在3.5~6.5V的工作电压下,可以高效稳定的发出明亮的绿光。可应用于交通信号灯、手机显示屏、节假日灯饰品等显示和照明领域。同时采用紫外光激发也可发出明亮的绿光。A method for a green light perovskite light emitting diode based on a surface post-treatment process can efficiently and stably emit bright green light at an operating voltage of 3.5-6.5V. It can be used in display and lighting fields such as traffic lights, mobile phone displays, holiday lighting accessories, etc. At the same time, it can also emit bright green light when excited by ultraviolet light.
与现有的技术相比较,本发明存在的优势:Compared with the prior art, the present invention has the following advantages:
1)本发明基于表面后处理工艺的绿光钙钛矿发光二极管制备工艺简单、成本低廉、重复性好。1) The green light perovskite light-emitting diode based on the surface post-treatment process of the present invention has a simple preparation process, low cost and good repeatability.
2)本发明基于表面后处理工艺的绿光钙钛矿发光二极管,这种以丁基溴化胺作为表面钝化层来修饰钙钛矿发光层的方法文献还没报道过,通过实验测试,具有较低的启动电压,获得较高的发光亮度和发光效率,实现了良好的稳定性。2) The present invention is based on the green light perovskite light-emitting diode of the surface post-treatment process. This method of modifying the perovskite light-emitting layer with butylamine bromide as the surface passivation layer has not been reported in the literature. Through experimental tests, It has a lower starting voltage, obtains higher luminous brightness and luminous efficiency, and achieves good stability.
附图说明Description of drawings
图1、实施例1中制备的BABr表面钝化前后的钙钛矿层扫描电镜照片。Fig. 1. Scanning electron microscope photos of the perovskite layer before and after the surface passivation of the BABr prepared in Example 1.
图2、实施例1中制备的BABr表面钝化前后的钙钛矿层光致发光照片。Figure 2. Photoluminescence photos of the perovskite layer before and after the surface passivation of the BABr prepared in Example 1.
图3、实施例1中制备的BABr表面钝化前后的绿光钙钛矿发光二极管Luminance-V曲线。图4、实施例1中制备的BABr表面钝化前后绿光钙钛矿发光二极管的EQE-V曲线,插图为黑暗条件下器件的发光照片。Figure 3. Luminance-V curves of the green perovskite light-emitting diode before and after surface passivation of the BABr prepared in Example 1. Figure 4. The EQE-V curves of the green perovskite light-emitting diode before and after the surface passivation of the BABr prepared in Example 1, the inset is the luminescence photo of the device under dark conditions.
具体实施方式Detailed ways
以下结合附图和实例来对本发明作进一步说明,但本发明并不限于以下实施个例。The present invention will be further described below with reference to the accompanying drawings and examples, but the present invention is not limited to the following examples.
实施例1Example 1
1)空穴传输层的制备:1) Preparation of hole transport layer:
将购买的Al4083 PEDOT:PSS溶液用去离子水进行稀释,稀释比例为2:1(PEDOT:PSS 和去离子水体积比),通过旋涂的方式涂覆于洁净的ITO导电玻璃上,150℃退火15min后形成一层致密的PEDOT:PSS薄膜。Dilute the purchased Al4083 PEDOT:PSS solution with deionized water at a dilution ratio of 2:1 (volume ratio of PEDOT:PSS and deionized water), and coat it on clean ITO conductive glass by spin coating at 150°C A dense PEDOT:PSS film was formed after annealing for 15 min.
2)钙钛矿层的制备:2) Preparation of perovskite layer:
将溴化铯和溴化铅以摩尔比为1:1加入DMSO中,配制成浓度为0.2M的钙钛矿前驱体溶液。常温下搅拌12h,得到澄清透明的无色钙钛矿前驱体溶液。在氮气手套箱中,取70uL前驱体溶液采用一步旋涂法,转速为2000rpm,时间为2min,正数30s滴加反溶剂150μL,得到的钙钛矿薄膜在加热板上100℃退火20min,冷却至室温。然在表面旋涂7mg/mL丁基溴化胺溶液(溶剂为异丙醇),转速为3000rpm,时间40s,经90℃退火10min后得到表面钝化的钙钛矿薄膜。Cesium bromide and lead bromide were added into DMSO at a molar ratio of 1:1 to prepare a perovskite precursor solution with a concentration of 0.2 M. Stir at room temperature for 12 h to obtain a clear and transparent colorless perovskite precursor solution. In a nitrogen glove box, 70uL of the precursor solution was taken by one-step spin coating method, the speed was 2000rpm, the time was 2min, and 150μL of anti-solvent was added dropwise for a positive number of 30s. to room temperature. Then spin-coat 7mg/mL butylamine bromide solution (solvent is isopropanol) on the surface, rotate speed is 3000rpm, time is 40s, and after annealing at 90℃ for 10min, the surface passivation perovskite film is obtained.
3)电子传输层的制备:3) Preparation of electron transport layer:
将电子传输层通过真空蒸镀沉积于步骤2)中的薄膜上,蒸发速率保持在厚度为40nm。The electron transport layer was deposited on the film in step 2) by vacuum evaporation, and the evaporation rate was kept at The thickness is 40nm.
4)电极修饰层/铝电极的制备:4) Preparation of electrode modification layer/aluminum electrode:
将电极修饰层氟化锂和铝电极通过真空蒸镀沉积于步骤3)中的薄膜上,蒸发速率分别为和厚度分别为1nm和80nm。The electrode modification layer lithium fluoride and aluminum electrode are deposited on the film in step 3) by vacuum evaporation, and the evaporation rates are respectively and The thicknesses are 1 nm and 80 nm, respectively.
制作的钙钛矿发光二极管在3.5~6.5V的工作电压内实现了稳定高效的电致发光,目前在无添加剂修饰的绿光钙钛矿发光二极管中处于较好的水平。The fabricated perovskite light-emitting diode achieves stable and high-efficiency electroluminescence within the working voltage of 3.5-6.5V, and is currently at a better level among green light-emitting perovskite light-emitting diodes modified without additives.
从图1可以看出经BABr表面钝化后钙钛矿薄膜生长情况,表面针孔数量显著降低,覆盖率明显提高。It can be seen from Figure 1 that the growth of the perovskite film after BABr surface passivation, the number of surface pinholes is significantly reduced, and the coverage is significantly improved.
从图2可以看出在紫外光激发的条件下,经BABr表面钝化后钙钛矿薄膜发出明亮的绿光,说明钙钛矿层中缺陷态密度显著降低,提升了有效的辐射复合所占的比例(下面右侧的块体的绿光亮度要远远高于下面左侧的块体的绿光亮度)。It can be seen from Figure 2 that under the condition of ultraviolet light excitation, the perovskite film emits bright green light after the surface passivation of BABr, indicating that the density of defect states in the perovskite layer is significantly reduced, which increases the proportion of effective radiation recombination. Scale (the block on the right below has a much higher green brightness than the block on the left below).
从图3可以看出BABr表面钝化的绿光钙钛矿发光二极管器件发光性能得到了显著提高,器件启动电压从4.3V降低到3.0V,说明钙钛矿薄膜致密性提高使器件工作时漏电流减小;最大亮度从23cd/m2提高到3296cd/m2。It can be seen from Figure 3 that the luminescence performance of the green perovskite light-emitting diode device with passivation on the surface of BABr has been significantly improved, and the device startup voltage has been reduced from 4.3V to 3.0V, indicating that the increase in the density of the perovskite film makes the device leak during operation. Current decreased; maximum brightness increased from 23cd/m 2 to 3296cd/m 2 .
从图4可以看出BABr表面钝化的绿光钙钛矿发光二极管器件发光效率得到了显著提高, EQE从0.08%提高到3.90%。It can be seen from Figure 4 that the luminous efficiency of the green perovskite light-emitting diode device with BABr surface passivation has been significantly improved, and the EQE has been increased from 0.08% to 3.90%.
同时测得在室温25℃、湿度为35-40%的条件下器件发光的半衰期为60s左右。At the same time, it is measured that the half-life of the device is about 60s at room temperature of 25°C and humidity of 35-40%.
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