CN114784215A - Preparation method of quasi-two-dimensional blue light LED device - Google Patents

Preparation method of quasi-two-dimensional blue light LED device Download PDF

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CN114784215A
CN114784215A CN202210336424.XA CN202210336424A CN114784215A CN 114784215 A CN114784215 A CN 114784215A CN 202210336424 A CN202210336424 A CN 202210336424A CN 114784215 A CN114784215 A CN 114784215A
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白雪
张富俊
张宇
武振南
陆敏
郜艳波
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Jilin University
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Abstract

The invention is suitable for the field of light emitting diodes, and provides a preparation method of a quasi-two-dimensional blue light LED device. In the preparation process of the device, the metal nanoclusters are mixed with the traditional transmission layer, and the electrical property of the original transmission layer is adjusted, so that the effect of balancing carrier transmission is realized, the performance of the perovskite light-emitting device is improved finally, the preparation method has the advantages of simple preparation process and high efficiency, and the problem of low efficiency of the existing blue light quasi-two-dimensional LED device is solved.

Description

一种准二维蓝光LED器件的制备方法A kind of preparation method of quasi-two-dimensional blue LED device

技术领域technical field

本发明属于发光二极管领域,尤其涉及一种准二维蓝光LED器件的制备方法。The invention belongs to the field of light emitting diodes, and in particular relates to a preparation method of a quasi-two-dimensional blue light LED device.

背景技术Background technique

准二维金属卤化物钙钛矿材料由于其高光致发光量子产率、可调节的光学带隙、优异的色纯度和低成本的溶液加工性,在发光二极管和显示应用领域具有广阔的前景。Quasi-2D metal halide perovskite materials hold great promise in light-emitting diode and display applications due to their high photoluminescence quantum yield, tunable optical bandgap, excellent color purity, and low-cost solution processability.

但是目前以钙钛矿材料作为发光层的发光二极管的光电性质仍远低于有机发光二极管。一方面是由于钙钛矿薄膜溶液结晶过程难以控制,造成薄膜结晶质量较差、相分布不均匀,造成过低的能量传输效率,从而产生过多的非辐射复合缺陷;另一方面是没有能级合适的传输层导致载流子注入困难,使得器件中载流子传输不平衡,导致器件的效率低,从而严重制约了钙钛矿薄膜及其设备的产业化应用。对于准二维蓝光LED器件来说,由于蓝光发光带隙大,导致其HOMO能级较深,没有兼具合适迁移率和能级的空穴传输材料一直是困扰准二维蓝光LED器件效率进一步提升的主要原因之一,为此我们提出一种准二维蓝光LED器件的制备方法。However, the photoelectric properties of light-emitting diodes using perovskite materials as light-emitting layers are still far lower than those of organic light-emitting diodes. On the one hand, the crystallization process of the perovskite film solution is difficult to control, resulting in poor crystalline quality and uneven phase distribution of the film, resulting in too low energy transmission efficiency, resulting in excessive non-radiative recombination defects; on the other hand, there is no energy. A suitable transport layer leads to the difficulty of carrier injection, which makes the carrier transport in the device unbalanced, resulting in low device efficiency, which seriously restricts the industrial application of perovskite thin films and their devices. For quasi-2D blue LED devices, due to the large band gap of blue light emission, the HOMO energy level is relatively deep, and the lack of hole transport materials with suitable mobility and energy level has been a problem for the efficiency of quasi-2D blue LED devices. One of the main reasons for the improvement is that we propose a fabrication method for quasi-two-dimensional blue LED devices.

发明内容SUMMARY OF THE INVENTION

本发明实施例的目的在于提供一种准二维蓝光LED器件的制备方法,旨在解决上述背景技术中提出的问题。The purpose of the embodiments of the present invention is to provide a preparation method of a quasi-two-dimensional blue LED device, which aims to solve the problems raised in the above background technology.

为实现上述目的,本发明提供如下技术方案:To achieve the above object, the present invention provides the following technical solutions:

一种准二维蓝光LED器件的制备方法,包括以下步骤:A preparation method of a quasi-two-dimensional blue LED device, comprising the following steps:

步骤1:将ITO基底,分别用去离子水、乙醇以及丙酮反复清洗,接着采用紫外臭氧机清洗20分钟;Step 1: The ITO substrate was repeatedly cleaned with deionized water, ethanol and acetone, and then cleaned with an ultraviolet ozone machine for 20 minutes;

步骤2:将PEDOT:PSS溶液采用旋转涂布的方式沉积到步骤1中基底的表面,用150℃进行后期退火,将导电聚合物、金属纳米团簇和导电聚合物的混合材料溶于有机试剂后,通过旋转涂布法沉积在基底表面,用150℃进行后期退火;Step 2: The PEDOT:PSS solution is deposited on the surface of the substrate in step 1 by spin coating, and post-annealing is performed at 150 °C, and the mixed material of conductive polymer, metal nanocluster and conductive polymer is dissolved in organic reagents After that, it was deposited on the surface of the substrate by spin coating, and then annealed at 150 °C;

步骤3:将适量的碘化铅、苯丁基溴化铵和溴化铯溶解到1毫升的DMSO溶液中,形成钙钛矿前体溶液;Step 3: Dissolve an appropriate amount of lead iodide, phenylbutylammonium bromide and cesium bromide into 1 ml of DMSO solution to form a perovskite precursor solution;

步骤4:将适量的步骤3中的钙钛矿前体溶液,滴加到步骤2的基底表面,然后采用旋转涂布的方式制备薄膜,在一定时间下,将150微升反溶剂滴加到钙钛矿薄膜表面,反溶剂为乙酸乙酯、氯苯和甲苯中的一种,从而使薄膜快速结晶,随后将薄膜放到加热台上进行后期的退火结晶;Step 4: Add an appropriate amount of the perovskite precursor solution in step 3 dropwise to the surface of the substrate in step 2, and then prepare a thin film by spin coating, and add 150 microliters of anti-solvent dropwise to the surface of the substrate for a certain period of time. On the surface of the perovskite film, the anti-solvent is one of ethyl acetate, chlorobenzene and toluene, so that the film is rapidly crystallized, and then the film is placed on a heating table for later annealing and crystallization;

步骤5:将步骤4获得的薄膜放到蒸镀仪中,蒸镀电子传输层和金属铝电极。Step 5: Put the thin film obtained in Step 4 into an evaporation apparatus, and evaporate the electron transport layer and the metal aluminum electrode.

进一步的,所述步骤2中,导电聚合物为PVK、Poly-TPD、PTAA和TFB中的一种。Further, in the step 2, the conductive polymer is one of PVK, Poly-TPD, PTAA and TFB.

进一步的,所述步骤2中,金属纳米团簇和导电聚合物的混合材料中,金属纳米团簇为油溶性金纳米团簇、油溶性银纳米团簇和油溶性铜纳米团簇中的一种。Further, in the step 2, in the mixed material of the metal nanocluster and the conductive polymer, the metal nanocluster is one of oil-soluble gold nanoclusters, oil-soluble silver nanoclusters and oil-soluble copper nanoclusters. kind.

进一步的,所述步骤2中,金属纳米团簇和导电聚合物的混合材料中,金属纳米团簇占混合材料的比例为5%-55%。Further, in the step 2, in the mixed material of the metal nanoclusters and the conductive polymer, the proportion of the metal nanoclusters in the mixed material is 5%-55%.

进一步的,所述金属纳米团簇用于提升空穴导电性。Further, the metal nanoclusters are used to improve hole conductivity.

进一步的,所述步骤2中,有机试剂为DMSO、DMF、CB和间二甲苯中的一种。Further, in the step 2, the organic reagent is one of DMSO, DMF, CB and m-xylene.

进一步的,所述步骤5中,电子传输材料为TPBi/LiF、TPBi/Liq、Tmpypb/LiF和Tmpypb/Liq中的一种。Further, in the step 5, the electron transport material is one of TPBi/LiF, TPBi/Liq, Tmpypb/LiF and Tmpypb/Liq.

与现有技术相比,本发明的有益效果是:Compared with the prior art, the beneficial effects of the present invention are:

该准二维蓝光LED器件的制备方法,将油溶性的金属纳米团簇掺杂进入有机导电聚合物中,有效地提升准二维蓝光LED器件的空穴载流子的注入与传输;利用金属纳米团簇地分子态特性,使得金属能够以另一种方式掺杂进入传输层中,利用其金属性提升导电聚合物导电性及载流子迁移率,同时利用金属纳米团簇的配体与导电聚合物中苯环之间的π-π堆叠,使得空穴传输层的HOMO能级与准二维蓝光钙钛矿发光层的HOMO能级之间的能级差更小,提升空穴的注入效率。In the preparation method of the quasi-two-dimensional blue LED device, oil-soluble metal nanoclusters are doped into an organic conductive polymer to effectively improve the injection and transport of hole carriers in the quasi-two-dimensional blue LED device; using metal The molecular properties of nanoclusters allow metals to be doped into the transport layer in another way, using their metallicity to improve the conductivity and carrier mobility of conductive polymers, and at the same time using the ligands of metal nanoclusters to interact with the transport layer. The π-π stacking between benzene rings in the conductive polymer makes the energy level difference between the HOMO energy level of the hole transport layer and the HOMO energy level of the quasi-2D blue perovskite light-emitting layer smaller, which improves the injection of holes. efficiency.

附图说明Description of drawings

图1为本发明实施例的实验优化前后薄膜粗糙度对比图。FIG. 1 is a comparison diagram of film roughness before and after experimental optimization in an embodiment of the present invention.

图2为本发明实施例中实验优化前后薄膜电导率对比图。FIG. 2 is a comparison diagram of the electrical conductivity of thin films before and after experimental optimization in the embodiment of the present invention.

图3为本发明实施例中实验优化前后薄膜载流子迁移率对比图。FIG. 3 is a comparison diagram of the carrier mobility of thin films before and after experimental optimization in an embodiment of the present invention.

图4为本发明实施例中实验优化前后器件电流密度及开启电压对比图。FIG. 4 is a comparison diagram of device current density and turn-on voltage before and after experimental optimization in an embodiment of the present invention.

具体实施方式Detailed ways

为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

以下结合具体实施例对本发明的具体实现进行详细描述。The specific implementation of the present invention will be described in detail below with reference to specific embodiments.

实施例1Example 1

本发明一个实施例提供的一种准二维蓝光LED器件的制备方法,包括以下步骤:An embodiment of the present invention provides a method for preparing a quasi-two-dimensional blue LED device, comprising the following steps:

步骤1:将ITO基底,分别用去离子水、乙醇以及丙酮反复清洗,接着采用紫外臭氧机清洗20分钟;Step 1: The ITO substrate was repeatedly cleaned with deionized water, ethanol and acetone, and then cleaned with an ultraviolet ozone machine for 20 minutes;

步骤2:将PEDOT:PSS溶液采用旋转涂布的方式沉积到步骤1中基底的表面,用150℃进行后期退火;Step 2: deposit the PEDOT:PSS solution on the surface of the substrate in step 1 by spin coating, and perform post-annealing at 150°C;

步骤3:将适量TFB溶于CB中,在氮气手套箱中使用旋转涂布的方式沉积到步骤2的基底表面,用150℃进行后期退火;Step 3: Dissolve an appropriate amount of TFB in CB, deposit it on the substrate surface of Step 2 by spin coating in a nitrogen glove box, and perform post-annealing at 150°C;

步骤4:将适量PVK与油溶性银纳米团簇溶于CB中,在氮气手套箱中使用旋转涂布的方式沉积到步骤3的基底表面,用150℃进行后期退火;Step 4: Dissolve an appropriate amount of PVK and oil-soluble silver nanoclusters in CB, deposit on the substrate surface of Step 3 by spin coating in a nitrogen glove box, and perform post-annealing at 150°C;

步骤5:将适量的碘化铅、苯丁基溴化铵和溴化铯溶解到1毫升的DMSO溶液中,形成钙钛矿前体溶液;Step 5: Dissolve an appropriate amount of lead iodide, phenylbutylammonium bromide and cesium bromide into 1 ml of DMSO solution to form a perovskite precursor solution;

步骤6:将适量步骤5中的钙钛矿前体溶液,滴加到步骤4的基底表面,然后采用旋转涂布的方式制备薄膜,在一定时间下,将150微升乙酸乙酯作为反溶剂,滴加到钙钛矿薄膜表面,从而使薄膜快速结晶,随后将薄膜放到加热台上进行后期的退火结晶;Step 6: Add an appropriate amount of the perovskite precursor solution in Step 5 to the surface of the substrate in Step 4, and then prepare a thin film by spin coating, using 150 microliters of ethyl acetate as an anti-solvent for a certain period of time , dropwise onto the surface of the perovskite film, so that the film crystallizes rapidly, and then the film is placed on a heating table for later annealing and crystallization;

步骤7:将步骤6获得的薄膜放到蒸镀仪中,蒸镀电子传输层TPBi/Liq和金属铝电极。Step 7: Put the film obtained in Step 6 into an evaporation apparatus, and evaporate the electron transport layer TPBi/Liq and the metal aluminum electrode.

本发明实施例中,钙钛矿薄膜是由准二维钙钛矿薄膜组成,准二维薄膜使用在三维钙钛矿中加入长链有机集团构建从而增强量子限域效应,是得器件发光峰位蓝移;优选的,金属纳米团簇的掺入不能使得优化后的传输层薄膜粗糙度与优化之前增加超过50%,并且利用旋转涂布法制备的钙钛矿层薄膜粗糙度与优化之前增加不能超过50%;金属纳米团簇的掺入提升空穴导电性、改善能级使得空穴传输层和发光层能级更匹配从而使得空穴注入效率提升,具体表现为开启电压(亮度为1坎德拉每平方米的电压)的降低。参见图1-图4,将银纳米团簇作为掺杂剂掺入导电聚合物PVK中作为空穴传输层,提升了PVK的空穴迁移率,改善PVK的能级,实现能级匹配的载流子注入,提升了载流子注入效率。金属纳米团簇因其过渡尺度兼具金属性和分子态特性,能够解决无机银盐和和有机配体单独作用的局限性,是一种非常良好的改善传输材料的方式。通过合适浓度掺杂,金属纳米粒子不会大幅度改善传输层的成膜特性,并且不会影响钙钛矿的成膜特性。利用银纳米团簇的掺杂可以明显增强空穴载流子的传输与注入,构筑平衡的载流子传输,实现了高亮度高效率的蓝光LED器件性能。In the embodiment of the present invention, the perovskite film is composed of a quasi-two-dimensional perovskite film, and the quasi-two-dimensional film is constructed by adding long-chain organic groups to the three-dimensional perovskite to enhance the quantum confinement effect, which is the luminescence peak of the device. blue-shift; preferably, the incorporation of metal nanoclusters cannot increase the roughness of the optimized transport layer film by more than 50% compared with that before optimization, and the roughness of the perovskite layer film prepared by spin coating method is increased compared with that before optimization. It cannot exceed 50%; the incorporation of metal nanoclusters improves hole conductivity, improves energy levels, and makes the energy levels of the hole transport layer and the light-emitting layer more matched, thereby improving the hole injection efficiency, which is manifested in the turn-on voltage (brightness of 1 candela voltage per square meter). Referring to Figures 1 to 4, silver nanoclusters are incorporated into the conductive polymer PVK as a dopant as a hole transport layer, which improves the hole mobility of PVK, improves the energy level of PVK, and realizes energy-level matched loading. The carrier injection improves the carrier injection efficiency. Metal nanoclusters are a very good way to improve transport materials because they have both metallic and molecular properties at the transition scale, which can solve the limitations of inorganic silver salts and organic ligands acting alone. By doping at a suitable concentration, the metal nanoparticles will not greatly improve the film-forming properties of the transport layer, and will not affect the film-forming properties of perovskite. The doping of silver nanoclusters can significantly enhance the transport and injection of hole carriers, build a balanced carrier transport, and achieve high-brightness and high-efficiency blue LED device performance.

实施例2Example 2

本发明一个实施例提供的一种准二维蓝光LED器件的制备方法,包括以下步骤:An embodiment of the present invention provides a method for preparing a quasi-two-dimensional blue LED device, comprising the following steps:

步骤1:将ITO基底,分别用去离子水、乙醇以及丙酮反复清洗,接着采用紫外臭氧机清洗20分钟;Step 1: The ITO substrate was repeatedly cleaned with deionized water, ethanol and acetone, and then cleaned with an ultraviolet ozone machine for 20 minutes;

步骤2:将PEDOT:PSS溶液采用旋转涂布的方式沉积到步骤1中基底的表面,用150℃进行后期退火;Step 2: deposit the PEDOT:PSS solution on the surface of the substrate in step 1 by spin coating, and perform post-annealing at 150°C;

步骤3:将适量Poly-TPD溶于间二甲苯中,在氮气手套箱中使用旋转涂布的方式沉积到步骤2的基底表面,用150℃进行后期退火;Step 3: Dissolve an appropriate amount of Poly-TPD in m-xylene, deposit it on the substrate surface of Step 2 by spin coating in a nitrogen glove box, and perform post-annealing at 150°C;

步骤4:将适量PTAA与油溶性铜纳米团簇溶于CB中,在氮气手套箱中使用旋转涂布的方式沉积到步骤3的基底表面,用150℃进行后期退火;Step 4: Dissolve an appropriate amount of PTAA and oil-soluble copper nanoclusters in CB, deposit them on the substrate surface of Step 3 by spin coating in a nitrogen glove box, and perform post-annealing at 150°C;

步骤5:将适量的碘化铅、苯丁基溴化铵和溴化铯溶解到1毫升的DMSO溶液中,形成钙钛矿前体溶液;Step 5: Dissolve an appropriate amount of lead iodide, phenylbutylammonium bromide and cesium bromide into 1 ml of DMSO solution to form a perovskite precursor solution;

步骤6:将适量步骤5中的钙钛矿前体溶液,滴加到步骤4的基底表面,然后采用旋转涂布的方式制备薄膜,在一定时间下,将150微升氯苯作为反溶剂,滴加到钙钛矿薄膜表面,从而使薄膜快速结晶,随后将薄膜放到加热台上进行后期的退火结晶;Step 6: Add an appropriate amount of the perovskite precursor solution in Step 5 to the surface of the substrate in Step 4, and then prepare a thin film by spin coating. For a certain period of time, use 150 microliters of chlorobenzene as an anti-solvent, It is added dropwise to the surface of the perovskite film to rapidly crystallize the film, and then the film is placed on a heating table for later annealing and crystallization;

步骤7:将步骤6获得的薄膜放到蒸镀仪中,蒸镀电子传输层TPBi/LiF和金属铝电极。Step 7: Put the film obtained in Step 6 into an evaporation apparatus, and evaporate the electron transport layer TPBi/LiF and the metal aluminum electrode.

实施例3Example 3

本发明一个实施例提供的一种准二维蓝光LED器件的制备方法,包括以下步骤:An embodiment of the present invention provides a method for preparing a quasi-two-dimensional blue LED device, comprising the following steps:

步骤1:将ITO基底,分别用去离子水、乙醇以及丙酮反复清洗,接着采用紫外臭氧机清洗20分钟;Step 1: The ITO substrate was repeatedly cleaned with deionized water, ethanol and acetone, and then cleaned with an ultraviolet ozone machine for 20 minutes;

步骤2:将PEDOT:PSS溶液采用旋转涂布的方式沉积到步骤1中基底的表面,用150℃进行后期退火;Step 2: deposit the PEDOT:PSS solution on the surface of the substrate in step 1 by spin coating, and perform post-annealing at 150°C;

步骤3:将适量TFB溶于DMSO中,在氮气手套箱中使用旋转涂布的方式沉积到步骤2的基底表面,用150℃进行后期退火;Step 3: Dissolve an appropriate amount of TFB in DMSO, deposit it on the substrate surface of Step 2 by spin coating in a nitrogen glove box, and perform post-annealing at 150°C;

步骤4:将适量Poly-TPD与油溶性铜纳米团簇溶于CB中,在氮气手套箱中使用旋转涂布的方式沉积到步骤3的基底表面,用150℃进行后期退火;Step 4: Dissolve an appropriate amount of Poly-TPD and oil-soluble copper nanoclusters in CB, deposit on the substrate surface of Step 3 by spin coating in a nitrogen glove box, and perform post-annealing at 150°C;

步骤5:将适量的碘化铅、苯丁基溴化铵和溴化铯溶解到1毫升的DMSO溶液中,形成钙钛矿前体溶液;Step 5: Dissolve an appropriate amount of lead iodide, phenylbutylammonium bromide and cesium bromide into 1 ml of DMSO solution to form a perovskite precursor solution;

步骤6:将适量步骤5中的钙钛矿前体溶液,滴加到步骤4的基底表面,然后采用旋转涂布的方式制备薄膜,在一定时间下,将150微升乙酸乙酯作为反溶剂,滴加到钙钛矿薄膜表面,从而使薄膜快速结晶,随后将薄膜放到加热台上进行后期的退火结晶;Step 6: Add an appropriate amount of the perovskite precursor solution in Step 5 to the surface of the substrate in Step 4, and then prepare a thin film by spin coating, using 150 microliters of ethyl acetate as an anti-solvent for a certain period of time , dropwise onto the surface of the perovskite film, so that the film crystallizes rapidly, and then the film is placed on a heating table for later annealing and crystallization;

步骤7:将步骤6获得的薄膜放到蒸镀仪中,蒸镀电子传输层TPBi/Liq和金属铝电极。Step 7: Put the film obtained in Step 6 into an evaporation apparatus, and evaporate the electron transport layer TPBi/Liq and the metal aluminum electrode.

实施例4Example 4

本发明一个实施例提供的一种准二维蓝光LED器件的制备方法,包括以下步骤:An embodiment of the present invention provides a method for preparing a quasi-two-dimensional blue LED device, comprising the following steps:

步骤1:将ITO基底,分别用去离子水、乙醇以及丙酮反复清洗,接着采用紫外臭氧机清洗20分钟;Step 1: The ITO substrate was repeatedly cleaned with deionized water, ethanol and acetone, and then cleaned with an ultraviolet ozone machine for 20 minutes;

步骤2:将PEDOT:PSS溶液采用旋转涂布的方式沉积到步骤1中基底的表面,用150℃进行后期退火;Step 2: deposit the PEDOT:PSS solution on the surface of the substrate in step 1 by spin coating, and perform post-annealing at 150°C;

步骤3:将适量TFB溶于DMSO中,在氮气手套箱中使用旋转涂布的方式沉积到步骤2的基底表面,用150℃进行后期退火;Step 3: Dissolve an appropriate amount of TFB in DMSO, deposit it on the substrate surface of Step 2 by spin coating in a nitrogen glove box, and perform post-annealing at 150°C;

步骤4:将适量PTAA与油溶性铜纳米团簇溶于CB中,在氮气手套箱中使用旋转涂布的方式沉积到步骤3的基底表面,用150℃进行后期退火;Step 4: Dissolve an appropriate amount of PTAA and oil-soluble copper nanoclusters in CB, deposit them on the substrate surface of Step 3 by spin coating in a nitrogen glove box, and perform post-annealing at 150°C;

步骤5:将适量的碘化铅、苯丁基溴化铵和溴化铯溶解到1毫升的DMSO溶液中,形成钙钛矿前体溶液;Step 5: Dissolve an appropriate amount of lead iodide, phenylbutylammonium bromide and cesium bromide into 1 ml of DMSO solution to form a perovskite precursor solution;

步骤6:将适量步骤5中的钙钛矿前体溶液,滴加到步骤4的基底表面,然后采用旋转涂布的方式制备薄膜,在一定时间下,将150微升乙酸乙酯作为反溶剂,滴加到钙钛矿薄膜表面,从而使薄膜快速结晶,随后将薄膜放到加热台上进行后期的退火结晶;Step 6: Add an appropriate amount of the perovskite precursor solution in Step 5 to the surface of the substrate in Step 4, and then prepare a thin film by spin coating, using 150 microliters of ethyl acetate as an anti-solvent for a certain period of time , dropwise onto the surface of the perovskite film, so that the film crystallizes rapidly, and then the film is placed on a heating table for later annealing and crystallization;

步骤7:将步骤6获得的薄膜放到蒸镀仪中,蒸镀电子传输层Tmpypb/Liq和金属铝电极。Step 7: Put the thin film obtained in Step 6 into an evaporation apparatus, and evaporate the electron transport layer Tmpypb/Liq and the metal aluminum electrode.

实施例5Example 5

本发明一个实施例提供的一种准二维蓝光LED器件的制备方法,包括以下步骤:An embodiment of the present invention provides a method for preparing a quasi-two-dimensional blue LED device, comprising the following steps:

步骤1:将ITO基底,分别用去离子水、乙醇以及丙酮反复清洗,接着采用紫外臭氧机清洗20分钟;Step 1: The ITO substrate was repeatedly cleaned with deionized water, ethanol and acetone, and then cleaned with an ultraviolet ozone machine for 20 minutes;

步骤2:将PEDOT:PSS溶液采用旋转涂布的方式沉积到步骤1中基底的表面,用150℃进行后期退火;Step 2: deposit the PEDOT:PSS solution on the surface of the substrate in step 1 by spin coating, and perform post-annealing at 150°C;

步骤3:将适量Poly-TPD溶于CB中,在氮气手套箱中使用旋转涂布的方式沉积到步骤2的基底表面,用150℃进行后期退火;Step 3: Dissolve an appropriate amount of Poly-TPD in CB, deposit it on the substrate surface of Step 2 by spin coating in a nitrogen glove box, and perform post-annealing at 150°C;

步骤4:将适量PVK与油溶性银纳米团簇溶于CB中,在氮气手套箱中使用旋转涂布的方式沉积到步骤3的基底表面,用150℃进行后期退火;Step 4: Dissolve an appropriate amount of PVK and oil-soluble silver nanoclusters in CB, deposit on the substrate surface of Step 3 by spin coating in a nitrogen glove box, and perform post-annealing at 150°C;

步骤5:将适量的碘化铅、苯丁基溴化铵和溴化铯溶解到1毫升的DMSO溶液中,形成钙钛矿前体溶液;Step 5: Dissolve an appropriate amount of lead iodide, phenylbutylammonium bromide and cesium bromide into 1 ml of DMSO solution to form a perovskite precursor solution;

步骤6:将适量步骤5中的钙钛矿前体溶液,滴加到步骤4的基底表面,然后采用旋转涂布的方式制备薄膜,在一定时间下,将150微升乙酸乙酯作为反溶剂,滴加到钙钛矿薄膜表面,从而使薄膜快速结晶,随后将薄膜放到加热台上进行后期的退火结晶;Step 6: Add an appropriate amount of the perovskite precursor solution in Step 5 to the surface of the substrate in Step 4, and then prepare a thin film by spin coating, using 150 microliters of ethyl acetate as an anti-solvent for a certain period of time , dropwise onto the surface of the perovskite film, so that the film crystallizes rapidly, and then the film is placed on a heating table for later annealing and crystallization;

步骤7:将步骤6获得的薄膜放到蒸镀仪中,蒸镀电子传输层Tmpypb/Liq和金属铝电极。Step 7: Put the thin film obtained in Step 6 into an evaporation apparatus, and evaporate the electron transport layer Tmpypb/Liq and the metal aluminum electrode.

实施例6Example 6

本发明一个实施例提供的一种准二维蓝光LED器件的制备方法,包括以下步骤:An embodiment of the present invention provides a method for preparing a quasi-two-dimensional blue LED device, comprising the following steps:

步骤1:将ITO基底,分别用去离子水、乙醇以及丙酮反复清洗,接着采用紫外臭氧机清洗20分钟;Step 1: The ITO substrate was repeatedly cleaned with deionized water, ethanol and acetone, and then cleaned with an ultraviolet ozone machine for 20 minutes;

步骤2:将PEDOT:PSS溶液采用旋转涂布的方式沉积到步骤1中基底的表面,用150℃进行后期退火;Step 2: deposit the PEDOT:PSS solution on the surface of the substrate in step 1 by spin coating, and perform post-annealing at 150°C;

步骤3:将适量PTAA与油溶性银纳米团簇溶于CB中,在氮气手套箱中使用旋转涂布的方式沉积到步骤2的基底表面,用150℃进行后期退火;Step 3: Dissolve an appropriate amount of PTAA and oil-soluble silver nanoclusters in CB, deposit on the substrate surface of Step 2 by spin coating in a nitrogen glove box, and perform post-annealing at 150°C;

步骤4:将适量的碘化铅、苯丁基溴化铵和溴化铯溶解到1毫升的DMSO溶液中,形成钙钛矿前体溶液;Step 4: Dissolve an appropriate amount of lead iodide, phenylbutylammonium bromide and cesium bromide into 1 ml of DMSO solution to form a perovskite precursor solution;

步骤5:将适量步骤4中的钙钛矿前体溶液,滴加到步骤3的基底表面,然后采用旋转涂布的方式制备薄膜,在一定时间下,将150微升乙酸乙酯作为反溶剂,滴加到钙钛矿薄膜表面,从而使薄膜快速结晶,随后将薄膜放到加热台上进行后期的退火结晶;Step 5: Add an appropriate amount of the perovskite precursor solution in step 4 to the surface of the substrate in step 3, and then prepare a thin film by spin coating, and use 150 microliters of ethyl acetate as an anti-solvent for a certain period of time. , dropwise onto the surface of the perovskite film, so that the film crystallizes rapidly, and then the film is placed on a heating table for later annealing and crystallization;

步骤6:将步骤5获得的薄膜放到蒸镀仪中,蒸镀电子传输层Tmpypb/Liq和金属铝电极。Step 6: Put the thin film obtained in Step 5 into an evaporation apparatus, and evaporate the electron transport layer Tmpypb/Liq and the metal aluminum electrode.

实施例7Example 7

本发明一个实施例提供的一种准二维蓝光LED器件的制备方法,包括以下步骤:An embodiment of the present invention provides a method for preparing a quasi-two-dimensional blue LED device, comprising the following steps:

步骤1:将ITO基底,分别用去离子水、乙醇以及丙酮反复清洗,接着采用紫外臭氧机清洗20分钟;Step 1: The ITO substrate was repeatedly cleaned with deionized water, ethanol and acetone, and then cleaned with an ultraviolet ozone machine for 20 minutes;

步骤2:将PEDOT:PSS溶液采用旋转涂布的方式沉积到步骤1中基底的表面,用150℃进行后期退火;Step 2: deposit the PEDOT:PSS solution on the surface of the substrate in step 1 by spin coating, and perform post-annealing at 150°C;

步骤3:将适量PVK与油溶性铜纳米团簇溶于DMF中,在氮气手套箱中使用旋转涂布的方式沉积到步骤2的基底表面,用150℃进行后期退火;Step 3: Dissolve an appropriate amount of PVK and oil-soluble copper nanoclusters in DMF, deposit them on the substrate surface of Step 2 by spin coating in a nitrogen glove box, and perform post-annealing at 150°C;

步骤4:将适量的碘化铅、苯丁基溴化铵和溴化铯溶解到1毫升的DMSO溶液中,形成钙钛矿前体溶液;Step 4: Dissolving an appropriate amount of lead iodide, phenylbutylammonium bromide and cesium bromide into 1 ml of DMSO solution to form a perovskite precursor solution;

步骤5:将适量步骤4中的钙钛矿前体溶液,滴加到步骤3的基底表面,然后采用旋转涂布的方式制备薄膜,在一定时间下,将150微升乙酸乙酯作为反溶剂,滴加到钙钛矿薄膜表面,从而使薄膜快速结晶,随后将薄膜放到加热台上进行后期的退火结晶;Step 5: Add an appropriate amount of the perovskite precursor solution in step 4 to the surface of the substrate in step 3, and then prepare a thin film by spin coating, and use 150 microliters of ethyl acetate as an anti-solvent for a certain period of time. , dropwise onto the surface of the perovskite film, so that the film crystallizes rapidly, and then the film is placed on a heating table for later annealing and crystallization;

步骤6:将步骤5获得的薄膜放到蒸镀仪中,蒸镀电子传输层Tmpypb/Liq和金属铝电极。Step 6: Put the thin film obtained in Step 5 into an evaporation apparatus, and evaporate the electron transport layer Tmpypb/Liq and the metal aluminum electrode.

本发明的工作原理是:The working principle of the present invention is:

该准二维蓝光LED器件的制备方法,将油溶性的金属纳米团簇掺杂进入有机导电聚合物中,有效地提升准二维蓝光LED器件的空穴载流子的注入与传输;利用金属纳米团簇地分子态特性,使得金属能够以另一种方式掺杂进入传输层中,利用其金属性提升导电聚合物导电性及载流子迁移率,同时利用金属纳米团簇的配体与导电聚合物中苯环之间的π-π堆叠,使得空穴传输层的HOMO能级与准二维蓝光钙钛矿发光层的HOMO能级之间的能级差更小,提升空穴的注入效率。In the preparation method of the quasi-two-dimensional blue LED device, oil-soluble metal nanoclusters are doped into an organic conductive polymer to effectively improve the injection and transport of hole carriers in the quasi-two-dimensional blue LED device; using metal The molecular properties of nanoclusters allow metals to be doped into the transport layer in another way, using their metallicity to improve the conductivity and carrier mobility of conductive polymers, and at the same time using the ligands of metal nanoclusters to interact with the transport layer. The π-π stacking between benzene rings in the conductive polymer makes the energy level difference between the HOMO energy level of the hole transport layer and the HOMO energy level of the quasi-2D blue perovskite light-emitting layer smaller, which improves the injection of holes. efficiency.

以上仅是本发明的优选实施方式,应当指出,对于本领域的技术人员来说,在不脱离本发明构思的前提下,还可以作出若干变形和改进,这些也应该视为本发明的保护范围,这些均不会影响本发明实施的效果和专利的实用性。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, some modifications and improvements can be made without departing from the concept of the present invention, and these should also be regarded as the protection scope of the present invention. , these will not affect the effect of the implementation of the present invention and the practicability of the patent.

Claims (7)

1. A preparation method of a quasi-two-dimensional blue light LED device is characterized by comprising the following steps:
step 1: repeatedly cleaning the ITO substrate by using deionized water, ethanol and acetone respectively, and then cleaning for 20 minutes by using an ultraviolet ozone machine;
step 2: PSS solution is deposited on the surface of the substrate in the step 1 in a spin coating mode, post annealing is carried out at 150 ℃, mixed materials of conductive polymers, metal nanoclusters and conductive polymers are dissolved in organic reagents and then deposited on the surface of the substrate through a spin coating method, and post annealing is carried out at 150 ℃;
and 3, step 3: dissolving a proper amount of lead iodide, phenylbutylammonium bromide and cesium bromide into 1 ml of DMSO solution to form a perovskite precursor solution;
and 4, step 4: dropwise adding a proper amount of the perovskite precursor solution obtained in the step 3 onto the surface of the substrate obtained in the step 2, preparing a film in a spin coating mode, dropwise adding 150 microliters of an anti-solvent onto the surface of the perovskite film within a certain time, wherein the anti-solvent is one of ethyl acetate, chlorobenzene and toluene, so that the film is rapidly crystallized, and then putting the film on a heating table for later annealing crystallization;
and 5: and (4) putting the film obtained in the step (4) into an evaporation instrument, and evaporating an electron transmission layer and a metal aluminum electrode.
2. The method for manufacturing a quasi-two-dimensional blue LED device according to claim 1, wherein in the step 2, the conductive polymer is one of PVK, Poly-TPD, PTAA and TFB.
3. The method for manufacturing a quasi-two-dimensional blue LED device according to claim 2, wherein in the step 2, the metal nanoclusters are one of oil-soluble gold nanoclusters, oil-soluble silver nanoclusters, and oil-soluble copper nanoclusters in the mixed material of the metal nanoclusters and the conductive polymer.
4. The method for manufacturing a quasi-two-dimensional blue light LED device according to claim 3, wherein in the step 2, the metal nanoclusters in the mixed material of the metal nanoclusters and the conductive polymer account for 5% -55% of the mixed material.
5. The method of claim 4, wherein the metal nanoclusters are used to enhance hole conductivity.
6. The method of claim 4, wherein in the step 2, the organic reagent is one of DMSO, DMF, CB and m-xylene.
7. The method of claim 1, wherein in step 5, the electron transport material is one of TPBi/LiF, TPBi/Liq, Tmpypb/LiF, and Tmpypb/Liq.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104681731A (en) * 2015-02-09 2015-06-03 南京工业大学 Perovskite type electroluminescent device and preparation method thereof
US20150318477A1 (en) * 2013-11-26 2015-11-05 Michael D. IRWIN Perovskite Material Layer Processing
CN109777415A (en) * 2019-03-22 2019-05-21 南京邮电大学 A kind of preparation method of high fluorescence quantum yield all-inorganic perovskite quantum dots
CN113130802A (en) * 2021-03-26 2021-07-16 华南理工大学 Blue light perovskite thin film, preparation thereof and inverted quasi-two-dimensional blue light perovskite light-emitting diode
CN113421966A (en) * 2021-06-08 2021-09-21 华南理工大学 Polyethylene oxide-doped quasi-two-dimensional perovskite thin film, preparation method thereof and light-emitting device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150318477A1 (en) * 2013-11-26 2015-11-05 Michael D. IRWIN Perovskite Material Layer Processing
CN104681731A (en) * 2015-02-09 2015-06-03 南京工业大学 Perovskite type electroluminescent device and preparation method thereof
CN109777415A (en) * 2019-03-22 2019-05-21 南京邮电大学 A kind of preparation method of high fluorescence quantum yield all-inorganic perovskite quantum dots
CN113130802A (en) * 2021-03-26 2021-07-16 华南理工大学 Blue light perovskite thin film, preparation thereof and inverted quasi-two-dimensional blue light perovskite light-emitting diode
CN113421966A (en) * 2021-06-08 2021-09-21 华南理工大学 Polyethylene oxide-doped quasi-two-dimensional perovskite thin film, preparation method thereof and light-emitting device

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