CN111740019A - Halide perovskite optoelectronic devices based on polar interfaces - Google Patents

Halide perovskite optoelectronic devices based on polar interfaces Download PDF

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CN111740019A
CN111740019A CN202010503089.9A CN202010503089A CN111740019A CN 111740019 A CN111740019 A CN 111740019A CN 202010503089 A CN202010503089 A CN 202010503089A CN 111740019 A CN111740019 A CN 111740019A
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perovskite
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连亚霄
赵保丹
狄大卫
理查德·亨利·弗兰德
崔林松
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Zhejiang University ZJU
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract

A halide perovskite photoelectric device based on a polar interface belongs to the technical field of novel energy, materials and electronics. The present invention is directed to a polar interface based halide perovskite optoelectronic device that efficiently matches perovskite material and charge transport material together through a polar interface material. The preparation process of the perovskite luminescent thin film luminescent device comprises the following steps: preparing a substrate with a polar interface; and transferring the substrate with the evaporated polar interface to a glove box filled with high-purity nitrogen to spin-coat the perovskite thin film to obtain the perovskite light-emitting thin film light-emitting device. The invention introduces a polar interface in the preparation process of the perovskite material and the photoelectric device, so that the charge transport material with excellent performance and the perovskite material are mutually compatible and effectively matched, the interface can regulate and control the potential barrier of the charge transport material and the perovskite, and can regulate and control the crystallization process of the perovskite on the substrate or the transport material to regulate and control the crystallization quality, and finally, the performance of the perovskite material and the photoelectric device is optimized or regulated and controlled.

Description

基于极性界面的卤化物钙钛矿光电器件Halide perovskite optoelectronic devices based on polar interfaces

技术领域technical field

本发明属于新型能源、材料和电子技术领域。The invention belongs to the technical fields of novel energy, materials and electronics.

背景技术Background technique

金属卤化物钙钛矿作为一种溶液法处理的材料,具有显著的光电特性,其中包括高载流子迁移率、较长的载流子扩散长度、可调整的带隙、高发光效率以及超窄发光带宽等优势方面。随着卤化物钙钛矿材料迅猛发展,钙钛矿的优异性能在很多应用方面取得巨大进展,例如在太阳能电池、光电探测器、发光二极管等光电器件方面得到广泛应用。2009年报道了第一个钙钛矿太阳能电池后,钙钛矿材料在太阳能电池领域得到飞速发展,2019年其能量转化效率已经超过25%。2014年报道了第一个钙钛矿发光器件后,在不到5年的时间里基于钙钛矿的发光器件性能迅速提升,2018年其外量子效率已经突破20%。其器件性能得到飞速发展是由于钙钛矿得到多个领域研究人员的广泛关注,人们致力于提升钙钛矿材料的整体性能,目前钙钛矿器件吸收了多个研究领域的宝贵经验,包括有机发光二极管、量子点发光二极管、半导体多晶硅电池、锂电池、高分子材料等多个领域,通过多方努力对钙钛矿及传输材料进行表面钝化和修饰,使得器件可有效抑制器件内部的非辐射复合且增强辐射复合,从而实现器件的性能大幅度提升。Metal halide perovskites, as a solution-processed material, exhibit remarkable optoelectronic properties, including high carrier mobility, long carrier diffusion length, tunable band gap, high luminescence efficiency, and ultra-high luminous efficiency. Narrow light-emitting bandwidth and other advantages. With the rapid development of halide perovskite materials, the excellent properties of perovskites have made great progress in many applications, such as solar cells, photodetectors, light-emitting diodes and other optoelectronic devices. After the first perovskite solar cell was reported in 2009, perovskite materials have developed rapidly in the field of solar cells, and their energy conversion efficiency has exceeded 25% in 2019. After the first perovskite light-emitting device was reported in 2014, the performance of perovskite-based light-emitting devices has rapidly improved in less than 5 years, and its external quantum efficiency has exceeded 20% in 2018. The rapid development of its device performance is due to the fact that perovskite has received extensive attention from researchers in many fields, and people are committed to improving the overall performance of perovskite materials. At present, perovskite devices have absorbed valuable experience in many research fields, including organic In many fields such as light-emitting diodes, quantum dot light-emitting diodes, semiconductor polysilicon batteries, lithium batteries, polymer materials, etc., the surface passivation and modification of perovskite and transmission materials have been made through various efforts, so that the device can effectively suppress the non-radiation inside the device. Recombination and enhanced radiation recombination, so as to achieve a substantial increase in the performance of the device.

目前器件结构也由最初始的三明治功能层演变为多层功能层,以五层结构为例,分别包括电极、空穴传输材料(电子阻挡材料)、发光材料(电池中为吸收材料)、电子传输材料(空穴阻挡材料)、电极。而对于功能材料的选取对于器件性能提高有积极作用,对于其它领域性能优异的材料,却不能直接适用于钙钛矿器件结构,仍需要做积极改进以适应钙钛矿器件结构,例如在溶液法处理钙钛矿发光器件中涉及到的多个功能材料间的溶剂与溶质互溶现象,这是期待解决的一个问题。At present, the structure of the device has also evolved from the original sandwich functional layer to a multi-layer functional layer. Taking the five-layer structure as an example, it includes electrodes, hole transport materials (electron blocking materials), light-emitting materials (absorbing materials in batteries), electron Transport materials (hole blocking materials), electrodes. The selection of functional materials has a positive effect on the improvement of device performance. For materials with excellent performance in other fields, they cannot be directly applied to the structure of perovskite devices. Active improvements are still needed to adapt to the structure of perovskite devices. For example, in the solution method Dealing with the mutual solubility of solvent and solute among multiple functional materials involved in perovskite light-emitting devices is a problem that is expected to be solved.

对于目前报道的OLED领域的具有突出性能的功能性材料,仍有较多材料不能以溶液法来直接制备高性能钙钛矿LED,要应用在钙钛矿领域还需进一步优化。如在制备发光二极管过程中,对于具有很强疏水性的空穴传输材料共轭聚合物TFB、Poly-TPD和PFO,很难让卤化物钙钛矿以溶液法沉积到上面。研究人员采用了多种方法以实现钙钛矿有效沉积到共轭聚合物上,一种方法是在沉积钙钛矿之前对TFB、Poly-TPD等空穴传输材料表面通过Plasma等离子体清洗机或UV-Ozone清洗机进行表面处理,从而将空穴传输材料表面由疏水性改为亲水性。然而,采用等离子体表面处理会给聚合物表面造成破坏进而引起导电特性的退化。另外一种方法是将很薄的PVK沉积到共轭聚合物上后再沉积钙钛矿,但是PVK可以溶解到DMF和DMSO中,而DMF和DMSO却是很常用的钙钛矿前驱体溶液,会导致钙钛矿沉积到PVK上时溶解部分PVK,造成PVK和钙钛矿形成共混界面,造成钙钛矿生长质量受到影响,引入界面缺陷和晶体生长缺陷,进而限制器件制备过程中的可靠性、稳定性。For the currently reported functional materials with outstanding performance in the OLED field, there are still many materials that cannot directly prepare high-performance perovskite LEDs by solution methods, and further optimization is required to apply them in the perovskite field. For example, in the process of fabricating light-emitting diodes, it is difficult for halide perovskites to be deposited on it by solution method for the highly hydrophobic hole transport materials conjugated polymers TFB, Poly-TPD and PFO. The researchers used a variety of methods to achieve efficient deposition of perovskites onto conjugated polymers. One method is to pass a Plasma plasma cleaner or a plasma cleaner on the surface of hole transport materials such as TFB, Poly-TPD, etc., before depositing the perovskite. UV-Ozone cleaning machine performs surface treatment, thereby changing the surface of the hole transport material from hydrophobic to hydrophilic. However, the use of plasma surface treatment can cause damage to the polymer surface resulting in degradation of the conductive properties. Another method is to deposit a very thin PVK onto a conjugated polymer and then deposit the perovskite, but PVK can be dissolved in DMF and DMSO, which are very commonly used perovskite precursor solutions. It will lead to the dissolution of part of PVK when perovskite is deposited on PVK, resulting in the formation of a blended interface between PVK and perovskite, which will affect the growth quality of perovskite, introduce interface defects and crystal growth defects, and then limit the reliability of the device preparation process. sex, stability.

发明内容SUMMARY OF THE INVENTION

本发明的目的是通过极性界面材料有效的将钙钛矿材料和电荷传输材料匹配在一起的基于极性界面的卤化物钙钛矿光电器件。The object of the present invention is a polar interface-based halide perovskite optoelectronic device that efficiently matches a perovskite material and a charge transport material together through a polar interface material.

本发明钙钛矿发光薄膜发光器件制备过程:The preparation process of the perovskite light-emitting thin film light-emitting device of the present invention:

衬底的制备:首先用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇七个步骤分别进行15分钟超声清洗,再将衬底放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗,随后将衬底转移到真空镀膜机中进行极性界面蒸镀,在真空镀膜机中的蒸镀过程均是在手套箱内完成,蒸镀后获得蒸镀有极性界面的衬底;Preparation of the substrate: firstly, ultrasonic cleaning was carried out for 15 minutes in seven steps of deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, and isopropanol, and then the substrate was placed in UV- Ozone cleaning was performed for 15 minutes in an Ozone ozone cleaning machine, and then the substrate was transferred to a vacuum coating machine for polar interface evaporation. The evaporation process in the vacuum coating machine was all completed in a glove box. Substrates coated with polar interfaces;

蒸镀有极性界面的衬底再转移到充满高纯氮的手套箱旋涂钙钛矿薄膜:旋涂钙钛矿时将蒸镀有极性界面的衬底放到真空旋涂机上,用移液枪吸取的钙钛矿前驱体溶液,滴到蒸镀有极性界面的衬底上,真空旋涂机以3000 rpm/s转速旋涂60 s,接着将旋涂完成钙钛矿的衬底放置到热台上进行60 ℃退火10 min,得到钙钛矿发光薄膜发光器件。The substrate with polar interface was evaporated and then transferred to a glove box filled with high-purity nitrogen. The perovskite precursor solution sucked by the pipette is dropped onto the substrate with polar interface, and the vacuum spin coater spins at 3000 rpm/s for 60 s, and then spins to complete the perovskite lining. The bottom was placed on a hot stage for annealing at 60 °C for 10 min to obtain a perovskite light-emitting thin film light-emitting device.

本发明极性界面材料由多种化合物构成,包括不同周期间可形成化合物的极性界面材料、不同族间可形成化合物的极性界面材料、不同族间可形成化合物的强极性界面材料、其它与钙钛矿材料相互配合的界面材料。The polar interface material of the present invention is composed of a variety of compounds, including polar interface materials that can form compounds in different periods, polar interface materials that can form compounds between different groups, strong polar interface materials that can form compounds between different groups, Other interface materials that cooperate with perovskite materials.

本发明不同周期间可形成化合物的极性界面材料包括金属氧化物材料界面ZrO2、V2O5、Al2O3、NiO、MoO3、ZnO、MgO、NiO、SnO2;不同族间可形成化合物的极性界面材料包括碳酸根金属化合物材料Li2CO3、Na2CO3、 Cs2CO3;不同族间可形成化合物的强极性界面材料包括金属氟化物材料界面LiF、NaF、KF、RbF、CsF、MgF2、CaF2;其它与钙钛矿材料相互配合的界面材料包括PTFE、压电薄膜、压电陶瓷。The polar interface materials that can form compounds during different periods of the present invention include metal oxide material interfaces ZrO 2 , V 2 O 5 , Al 2 O 3 , NiO, MoO 3 , ZnO, MgO, NiO, SnO 2 ; The polar interface materials that form compounds include carbonate metal compound materials Li 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 ; the strongly polar interface materials that can form compounds between different groups include metal fluoride material interfaces LiF, NaF, KF, RbF, CsF, MgF 2 , CaF 2 ; other interface materials that cooperate with perovskite materials include PTFE, piezoelectric films, and piezoelectric ceramics.

本发明制备带有ITO的可导电性钙钛矿发光薄膜发光器件:The present invention prepares a conductive perovskite light-emitting thin film light-emitting device with ITO:

a、带有ITO的可导电性衬底:ITO通过磁控溅射技术将ITO原料溅射到衬底上,将衬底放置到有掩膜版的基板台上,用掩膜版对衬底进行部分遮挡,暴露出来部分溅射上ITO材料;a. Conductive substrate with ITO: ITO sputters the ITO raw material onto the substrate through magnetron sputtering technology, places the substrate on the substrate stage with a mask, and uses the mask to align the substrate Partial shading is carried out, and part of the exposed ITO material is sputtered;

b、可导电性衬底的清洗处理:对于可导电性衬底需要进行前处理,首先用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇七个步骤分别进行15分钟超声清洗,再将可导电性衬底放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗;b. Cleaning treatment of conductive substrates: For conductive substrates, pretreatment is required. First, use deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, and isopropanol. Each step is ultrasonically cleaned for 15 minutes, and then the conductive substrate is placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning;

c、制备电荷传输材料薄膜:将清洗完成的可导电性衬底放置到玻璃培养皿中,并通过手套箱的过渡仓将玻璃培养皿传送进入氮气手套箱,然后将可导电性衬底放到氮气手套箱内的真空旋涂机上,电荷传输材料是溶解在溶剂中,用移液枪吸取电荷传输材料溶液均匀涂覆到可导电性的衬底上,电荷传输材料将ITO全部包覆起来,开启真空旋涂机按钮以3000rpm转速旋涂60s,形成电荷传输材料的薄膜,电荷传输材料薄膜旋涂完成后,将覆盖有电荷传输材料的可导电性衬底放置到热台上进行120℃高温退火,时间为10min,最终在可导电性衬底上形成包覆ITO的电荷传输材料薄膜;c. Preparation of charge transport material film: place the cleaned conductive substrate in a glass petri dish, and transfer the glass petri dish into a nitrogen glove box through the transition chamber of the glove box, and then place the conductive substrate in a glass petri dish. On the vacuum spin coater in the nitrogen glove box, the charge transport material is dissolved in the solvent, and the charge transport material solution is drawn with a pipette and uniformly coated on the conductive substrate, and the charge transport material completely coats the ITO. Turn on the vacuum spin coater button and spin at 3000rpm for 60s to form a film of the charge transport material. After the spin coating of the charge transport material film is completed, place the conductive substrate covered with the charge transport material on a hot stage for a high temperature of 120°C. Annealing for 10 minutes, and finally forming a thin film of charge transport material coated with ITO on the conductive substrate;

d、蒸镀极性界面材料:打开步骤一的手套箱内真空镀膜机的仓门,将从热台上取下的制备有电荷传输材料的可导电性衬底放置到玻璃培养皿中,通过过渡仓传送进入带有真空镀膜机的手套箱中,制备有电荷传输材料的可导电性衬底取出,放置到真空镀膜机中的蒸镀基板台上,调整好蒸镀基板台的位置,关闭基板台下方挡板;d. Evaporation of polar interface materials: Open the door of the vacuum coating machine in the glove box in step 1, and place the conductive substrate prepared with the charge transport material removed from the hot stage into a glass petri dish. The transition bin is transferred into the glove box with the vacuum coating machine, and the conductive substrate prepared with the charge transport material is taken out, placed on the evaporation substrate stage in the vacuum coating machine, adjusted the position of the evaporation substrate stage, and closed. baffle plate below the substrate stage;

e、旋涂卤化物钙钛矿薄膜:旋涂时将蒸镀有极性界面材料、覆盖有电荷传输材料的可导电性衬底放置到真空旋涂机上,用移液枪吸取的卤化物钙钛矿前驱体溶液均匀涂覆到蒸镀有极性界面材料、覆盖有电荷传输材料的可导电性衬底上,开启真空旋涂机的按钮以5000rpm转速旋涂60s,形成卤化物钙钛矿的薄膜,将覆盖有卤化物钙钛矿、蒸镀有极性界面材料、覆盖有电荷传输材料的可导电性衬底放置到热台上进行90℃高温退火,时间为10min;e. Spin-coating halide perovskite thin film: During spin-coating, place the conductive substrate evaporated with polar interface material and covered with charge-transporting material on a vacuum spin-coater, and use a pipette to absorb calcium halide. The titanium ore precursor solution was uniformly coated on the conductive substrate evaporated with polar interface material and covered with charge transport material, and the button of the vacuum spin coater was turned on and spun at 5000 rpm for 60 s to form halide perovskite. The conductive substrate covered with halide perovskite, evaporated with polar interface material, and covered with charge transport material was placed on a hot stage for high temperature annealing at 90°C for 10 minutes;

f、蒸镀阴极电荷传输材料:将退火完成的覆盖有卤化物钙钛矿、蒸镀有极性界面材料、覆盖有电荷传输材料的可导电性衬底放到玻璃培养皿中,并通过过渡仓传送进入带有真空镀膜机的手套箱中,将其由玻璃培养皿取出放置到真空镀膜机中的蒸镀基板台上,调整好蒸镀基板台的位置,关闭基板台下方挡板;通过膜厚仪显示出石英晶振片所检测的电荷传输材料的蒸发速率,等待膜厚仪显示的电荷传输材料的蒸发速率稳定后,蒸镀速率稳定在0.05nm/s,开启真空镀膜机中基板台下方的挡板,蒸发速率均匀的电荷传输材料可以均匀沉积到覆盖有卤化物钙钛矿、蒸镀有极性界面材料、覆盖有电荷传输材料的可导电性衬底上;f. Evaporation of cathode charge transport material: The annealed conductive substrate covered with halide perovskite, evaporated with polar interface material, and covered with charge transport material is placed in a glass petri dish and transferred The warehouse is transported into a glove box with a vacuum coating machine, taken out from a glass petri dish and placed on the evaporation substrate stage in the vacuum coating machine, adjust the position of the evaporation substrate stage, and close the baffle below the substrate stage; The film thickness meter shows the evaporation rate of the charge transport material detected by the quartz crystal oscillator. After waiting for the evaporation rate of the charge transport material displayed by the film thickness meter to stabilize, the evaporation rate is stabilized at 0.05nm/s, and the substrate stage in the vacuum coating machine is turned on. The baffle below, the charge transport material with uniform evaporation rate can be uniformly deposited on the conductive substrate covered with halide perovskite, evaporated with polar interface material, and covered with charge transport material;

g、蒸镀电极:蒸镀完成电荷传输材料后,在真空镀膜机内将其放置到金属掩膜版上,通过膜厚仪显示出石英晶振片所检测的电极的蒸发速率,等待膜厚仪显示的电极的蒸发速率稳定后,蒸镀速率稳定在0.2nm/s,开启真空镀膜机中基板台下方的挡板,蒸发速率均匀的电极均匀沉积到覆盖有电荷传输材料、卤化物钙钛矿、蒸镀有极性界面材料、覆盖有电荷传输材料的可导电性衬底上。g. Evaporation electrode: After the charge transport material is evaporated, place it on the metal mask in the vacuum coating machine, and display the evaporation rate of the electrode detected by the quartz crystal oscillator through the film thickness meter. Wait for the film thickness meter After the evaporation rate of the displayed electrode is stabilized, the evaporation rate is stabilized at 0.2 nm/s, and the baffle below the substrate stage in the vacuum coating machine is opened, and the electrode with uniform evaporation rate is uniformly deposited to the surface covered with charge transport material, halide perovskite , Evaporated on a conductive substrate with polar interface materials and covered with charge transport materials.

本发明衬底上的极性界面制备方法采用磁控溅射、MOCVD、ALD、喷涂、印刷或化学合成方法,厚度范围为0.1 nm ~ 1000 nm。The preparation method of the polar interface on the substrate of the present invention adopts magnetron sputtering, MOCVD, ALD, spraying, printing or chemical synthesis method, and the thickness ranges from 0.1 nm to 1000 nm.

本发明通过调控不同电负性之差的材料来改变极性界面材料的极性,或调控非极性界面为极性界面,最终通过改变材料界面极性方式进而调控器件最终性能。The invention changes the polarity of the polar interface material by regulating materials with different electronegativity differences, or regulates the non-polar interface to be a polar interface, and finally regulates the final performance of the device by changing the polarity of the material interface.

本发明极性材料界面应用于多种光电器件方面,包括太阳能电池、发光二极管、探测器、荧光薄膜、荧光粉、半导体晶体管、激光等光电子器件和材料方面。The polar material interface of the present invention is applied to various optoelectronic devices, including solar cells, light-emitting diodes, detectors, fluorescent films, phosphors, semiconductor transistors, lasers and other optoelectronic devices and materials.

本发明极性材料界面可以应用于定义钙钛矿材料或器件的有效工作面积,进而定义不同的工作图案,可扩展应用于基于不同图案的钙钛矿材料及光电器件。The polar material interface of the present invention can be applied to define the effective working area of perovskite materials or devices, and then define different working patterns, which can be extended to perovskite materials and optoelectronic devices based on different patterns.

本发明在钙钛矿材料及光电器件制备过程中引入极性界面,使得性能优异的电荷传输材料与钙钛矿材料相互兼容、有效匹配,界面既可调控电荷传输材料与钙钛矿的势垒,也可调控钙钛矿在衬底或者传输材料上的结晶过程以调控结晶质量,最终优化或调控钙钛矿材料及光电器件的性能。采用极性界面调控钙钛矿材料及光电器件的方法,可以拓展应用到多种光电器件与材料方面,包括太阳能电池、发光二极管、探测器、荧光薄膜、荧光粉、半导体晶体管、激光等光电子器件与材料方面。The invention introduces a polar interface in the preparation process of the perovskite material and the optoelectronic device, so that the charge transport material with excellent performance and the perovskite material are compatible and effectively matched with each other, and the interface can not only regulate the potential barrier between the charge transport material and the perovskite , the crystallization process of perovskite on substrates or transport materials can also be regulated to control the crystallization quality, and finally optimize or tune the performance of perovskite materials and optoelectronic devices. The method of controlling perovskite materials and optoelectronic devices using polar interfaces can be extended to a variety of optoelectronic devices and materials, including solar cells, light-emitting diodes, detectors, fluorescent films, phosphors, semiconductor transistors, lasers and other optoelectronic devices in terms of materials.

附图说明Description of drawings

图1是本发明普通衬底极性界面的钙钛矿结构;Fig. 1 is the perovskite structure of the polar interface of common substrate of the present invention;

图2是本发明带有ITO的可导电性衬底的极性界面钙钛矿光电器件结构;Fig. 2 is the polar interface perovskite photoelectric device structure of the conductive substrate with ITO of the present invention;

图3是本发明极性界面的亲水性实验制备流程图;Fig. 3 is the hydrophilic experiment preparation flow chart of the polar interface of the present invention;

图4是本发明添加界面前后的表面张力对比图;Fig. 4 is the surface tension contrast figure before and after adding interface of the present invention;

图5是本发明采用极性界面和等离子体分别进行表面处理流程图;Fig. 5 is the present invention adopts polar interface and plasma to carry out surface treatment flow chart respectively;

图6是本发明采用极性界面和等离子体表面处理的电荷传输材料形貌图;Fig. 6 is the topography of the charge transport material using polar interface and plasma surface treatment in the present invention;

图7是本发明旋涂钙钛矿发光薄膜查看SEM流程图;Fig. 7 is the SEM flow chart of the spin-coated perovskite luminescent film of the present invention;

图8是本发明钙钛矿在不同界面上成膜形貌SEM图;8 is a SEM image of the film-forming morphology of the perovskite of the present invention on different interfaces;

图9是本发明旋涂钙钛矿发光薄膜测试Wavelength流程图;Fig. 9 is the Wavelength flow chart of the spin-coated perovskite luminescent film test of the present invention;

图10是不同材料作为界面时的钙钛矿发光光谱图;Figure 10 is a perovskite luminescence spectrum when different materials are used as an interface;

图11是旋涂钙钛矿发光薄膜测试Absorbance流程图;Figure 11 is the flow chart of the Absorbance test of the spin-coated perovskite luminescent film;

图12是不同材料作为界面时对钙钛矿吸收光谱影响示意图;Figure 12 is a schematic diagram of the effect of different materials on the absorption spectrum of perovskite when used as an interface;

图13是旋涂钙钛矿发光薄膜测试XRD流程图;Fig. 13 is the XRD flow chart of the spin-coated perovskite luminescent film test;

图14是钙钛矿在不同界面上的薄膜XRD谱图;Fig. 14 is the thin film XRD patterns of perovskite on different interfaces;

图15是不同界面的光致量子效率PLQE测试流程图;Figure 15 is a flow chart of the photo-induced quantum efficiency PLQE test at different interfaces;

图16是钙钛矿的PLQE随不同极性界面电负性的变化图;Fig. 16 is a graph showing the change of PLQE of perovskite with interfacial electronegativity of different polarities;

图17是钙钛矿在不同电荷传输材料上的制备步骤流程图;Figure 17 is a flow chart of the preparation steps of perovskite on different charge transport materials;

图18是钙钛矿在不同电荷传输材料上的荧光寿命曲线图;Figure 18 is a graph showing the fluorescence lifetime of perovskite on different charge transport materials;

图19是不同厚度界面的制备流程图;Fig. 19 is the preparation flow chart of the interface of different thickness;

图20是不同厚度的界面对电荷注入能力的影响曲线图;Fig. 20 is a graph showing the effect of interfaces of different thicknesses on charge injection capability;

图21是发光二极管器件制备流程图;FIG. 21 is a flow chart of the fabrication of light-emitting diode devices;

图22是基于极性界面传输材料和其它传输材料的器件效率曲线图。Figure 22 is a graph of device efficiency based on polar interface transport materials and other transport materials.

具体实施方式Detailed ways

本发明钙钛矿发光薄膜发光器件制备过程:The preparation process of the perovskite light-emitting thin film light-emitting device of the present invention:

衬底的制备:首先用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇七个步骤分别进行15分钟超声清洗,再将衬底放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗,随后将衬底转移到真空镀膜机中进行极性界面蒸镀,在真空镀膜机中的蒸镀过程均是在手套箱内完成,蒸镀后获得蒸镀有极性界面的衬底;Preparation of the substrate: firstly, ultrasonic cleaning was carried out for 15 minutes in seven steps of deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, and isopropanol, and then the substrate was placed in UV- Ozone cleaning was performed for 15 minutes in an Ozone ozone cleaning machine, and then the substrate was transferred to a vacuum coating machine for polar interface evaporation. The evaporation process in the vacuum coating machine was all completed in a glove box. Substrates coated with polar interfaces;

蒸镀有极性界面的衬底再转移到充满高纯氮的手套箱旋涂钙钛矿薄膜:旋涂钙钛矿时将蒸镀有极性界面的衬底放到真空旋涂机上,用移液枪吸取的钙钛矿前驱体溶液,滴到蒸镀有极性界面的衬底上,真空旋涂机以3000 rpm/s转速旋涂60 s,接着将旋涂完成钙钛矿的衬底放置到热台上进行60 ℃退火10 min,得到钙钛矿发光薄膜发光器件。The substrate with polar interface was evaporated and then transferred to a glove box filled with high-purity nitrogen. The perovskite precursor solution sucked by the pipette is dropped onto the substrate with polar interface, and the vacuum spin coater spins at 3000 rpm/s for 60 s, and then spins to complete the perovskite lining. The bottom was placed on a hot stage for annealing at 60 °C for 10 min to obtain a perovskite light-emitting thin film light-emitting device.

本发明极性界面材料由多种化合物构成,包括不同周期间可形成化合物的极性界面材料、不同族间可形成化合物的极性界面材料、不同族间可形成化合物的强极性界面材料、其它与钙钛矿材料相互配合的界面材料。The polar interface material of the present invention is composed of a variety of compounds, including polar interface materials that can form compounds in different periods, polar interface materials that can form compounds between different groups, strong polar interface materials that can form compounds between different groups, Other interface materials that cooperate with perovskite materials.

本发明不同周期间可形成化合物的极性界面材料包括金属氧化物材料界面ZrO2、V2O5、Al2O3、NiO、MoO3、ZnO、MgO、NiO、SnO2;不同族间可形成化合物的极性界面材料包括碳酸根金属化合物材料Li2CO3、Na2CO3、 Cs2CO3;不同族间可形成化合物的强极性界面材料包括金属氟化物材料界面LiF、NaF、KF、RbF、CsF、MgF2、CaF2;其它与钙钛矿材料相互配合的界面材料包括PTFE、压电薄膜、压电陶瓷。The polar interface materials that can form compounds during different periods of the present invention include metal oxide material interfaces ZrO 2 , V 2 O 5 , Al 2 O 3 , NiO, MoO 3 , ZnO, MgO, NiO, SnO 2 ; The polar interface materials that form compounds include carbonate metal compound materials Li 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 ; the strongly polar interface materials that can form compounds between different groups include metal fluoride material interfaces LiF, NaF, KF, RbF, CsF, MgF 2 , CaF 2 ; other interface materials that cooperate with perovskite materials include PTFE, piezoelectric films, and piezoelectric ceramics.

为了解决钙钛矿中两种材料不匹配的问题,通过借鉴无机半导体领域和材料领域的相关研究经验。目前在三五族无机半导体中进行外延生长时,对于两种不同的半导体材料,当两种材料晶格参数相差较大会导致难以直接匹配,当晶格参数相差较小时虽然可以接触但会形成半导体异质结,由于晶格常数的差异会导致界面上产生大量界面态,这对异质结能带结构和电子输运产生很大的影响。故为了消除界面缺陷引起的材料难以生长的问题,并使得两种功能性材料良好接触,通过引入极性材料或活化材料在两种材料之间,可将两种材料间的肖特基接触改善为欧姆接触。引入的极性材料或活化材料使得两种功能材料晶格失配小、界面态密度低、界面势垒低,从而增加了电子注入及输运能力,故通过对界面进行有效处理可将不同材料进行有效配合。在金属玻璃制备工艺中,由于玻璃和金属的晶格不匹配,会导致制备出的金属玻璃稳定性不够好,故在玻璃和金属之间引入少量的过渡金属或石墨烯进行晶格匹配,可实现更稳定的晶格结构。基于此,针对钙钛矿中性能优异的电荷传输材料与钙钛矿材料不匹配的现象,可考虑引入功能材料或活化材料使得钙钛矿材料和电荷传输材料有效匹配,以降低界面的势垒、增加电子输运能力。In order to solve the problem of mismatch between the two materials in perovskite, the relevant research experience in the field of inorganic semiconductors and materials is used for reference. At present, when epitaxial growth is carried out in group III and V inorganic semiconductors, for two different semiconductor materials, when the lattice parameters of the two materials differ greatly, it will lead to difficulty in direct matching. In the heterojunction, a large number of interface states will be generated at the interface due to the difference of the lattice constant, which has a great influence on the band structure and electron transport of the heterojunction. Therefore, in order to eliminate the problem of difficult growth of materials caused by interface defects, and to make the two functional materials in good contact, the Schottky contact between the two materials can be improved by introducing polar materials or activated materials between the two materials. for ohmic contact. The introduction of polar materials or active materials makes the lattice mismatch of the two functional materials low, the interface state density is low, and the interface barrier is low, thereby increasing the electron injection and transport capabilities. cooperate effectively. In the preparation process of metallic glass, due to the mismatch between the lattices of glass and metal, the stability of the prepared metallic glass will not be good enough. Therefore, a small amount of transition metal or graphene is introduced between the glass and the metal for lattice matching, which can improve the stability of the prepared metallic glass. A more stable lattice structure is achieved. Based on this, in view of the mismatch between perovskite and perovskite materials with excellent performance, we can consider introducing functional materials or activation materials to effectively match perovskite and charge transport materials to reduce the interface barrier. , to increase the electronic transport capacity.

由于钙钛矿是强极性材料,根据相似相容原理,钙钛矿可以和强极性材料很好的配合,同时引入的新材料不能改变钙钛矿固有成分,故选取一些不同的强极性材料作为界面材料引入到电荷传输材料和钙钛矿材料之间进行晶格匹配。对于原位生长的钙钛矿需要不同的传输材料,但是性能优异的传输材料与钙钛矿不兼容,导致钙钛矿与传输材料界面存在电荷传输的障碍,通过采用超薄的强极性材料沉积到聚合物空穴传输材料上,可保证钙钛矿有效生长到覆盖有极性界面的聚合物空穴传输材料上,且采用极性材料界面可以增加或调控晶体生长的质量,调控钙钛矿薄膜的载流子寿命,进而调控薄膜的稳定性和基于钙钛矿的器件性能。采用极性界面来调控钙钛矿薄膜或器件性能的方法可以扩展应用到其它光电子器件方面,包括太阳能电池、发光二极管、探测器、荧光薄膜、荧光粉、半导体晶体管、激光等光电子器件与材料方面,以制备性能更优异的器件。Since perovskite is a strong polar material, according to the similar compatibility principle, perovskite can cooperate well with strong polar materials, and the new material introduced at the same time cannot change the inherent composition of perovskite, so some different strong polar materials are selected. The interfacial material is introduced into the charge transport material and the perovskite material for lattice matching. Different transport materials are required for in situ growth of perovskites, but the transport materials with excellent performance are incompatible with perovskites, resulting in the barrier of charge transport at the interface between perovskite and transport materials. By using ultra-thin strong polar materials Deposition on the polymer hole transport material can ensure that the perovskite is effectively grown on the polymer hole transport material covered with the polar interface, and the use of the polar material interface can increase or control the quality of the crystal growth and control the perovskite The carrier lifetime of the ore thin film, thereby regulating the stability of the thin film and the performance of perovskite-based devices. The method of using polar interfaces to modulate the performance of perovskite films or devices can be extended to other optoelectronic devices, including solar cells, light-emitting diodes, detectors, fluorescent films, phosphors, semiconductor transistors, lasers and other optoelectronic devices and materials. , in order to prepare devices with better performance.

目前钙钛矿材料及光电器件在光电性能和稳定性方面仍存在不足,具体原因表现为两方面,一方面是性能突出的衬底、电荷传输材料和钙钛矿材料不能完美匹配,限制了制备的钙钛矿光电器件的最优性能,例如对于溶液法制备的光电器件,电荷传输材料、钙钛矿材料存在界面互溶现象,导致界面不完美进而影响到各功能材料的性能;另一方面是钙钛矿材料本身存在问题,表现为晶体生长质量差、晶界及界面缺陷多,最终限制钙钛矿材料及光电器件的性能,目前在制备过程中可采用多种方法优化钙钛矿结晶质量,最终提高或调控钙钛矿材料及光电器件的性能。针对于钙钛矿材料和电荷传输材料不兼容的问题,目前常用的一种方法是利用Plasma表面清洗机或者UV-Ozone表面清洗机对电荷传输材料表面进行活化处理,经过处理的电荷传输材料表面得到活化,但是表面处理会破坏传输材料表面的基团结构,虽然可与钙钛矿表面基团更好结合,但是带来的问题是钙钛矿沉积到经过活化处理的电荷传输材料表面,钙钛矿本身性能如PLQE会不同程度的下降,且电荷传输材料的电荷传输能力也有不同程度下降。另外一种方法是用非正交溶剂引入中间材料作为钙钛矿材料和电荷传输材料的过渡材料,由于正交溶剂与钙钛矿材料相溶解会引起钙钛矿性能下降,钙钛矿溶剂溶解电荷传输材料会导致传输材料电荷传输能力下降,无论哪种溶剂对于材料都有不同程度破坏,这意味着对于不同的研究人员、不同的操作手法,其制备出来的器件与目标性能有很大不同,带来的结果便是器件重复性差、制备复杂性高、批量难度大。At present, perovskite materials and optoelectronic devices are still insufficient in terms of optoelectronic properties and stability. The specific reasons are two aspects. On the one hand, the outstanding performance of substrates, charge transport materials and perovskite materials cannot be perfectly matched, which limits the preparation. The optimal performance of perovskite optoelectronic devices, for example, for optoelectronic devices prepared by solution method, the charge transport material and perovskite material have interfacial mutual dissolution phenomenon, resulting in imperfect interface and affecting the performance of each functional material; on the other hand, The perovskite material itself has problems, which are manifested in poor crystal growth quality, many grain boundaries and interface defects, which ultimately limit the performance of perovskite materials and optoelectronic devices. At present, various methods can be used in the preparation process to optimize the perovskite crystal quality. , and ultimately improve or tune the performance of perovskite materials and optoelectronic devices. In view of the incompatibility between perovskite materials and charge transport materials, a commonly used method is to use a Plasma surface cleaner or a UV-Ozone surface cleaner to activate the surface of the charge transport material, and the treated surface of the charge transport material It is activated, but the surface treatment will destroy the group structure on the surface of the transport material. Although it can be better combined with the perovskite surface groups, the problem is that the perovskite is deposited on the surface of the activated charge transport material. The properties of titanium ore itself, such as PLQE , will decrease to varying degrees, and the charge transport ability of charge transport materials will also decrease to varying degrees. Another method is to use a non-orthogonal solvent to introduce an intermediate material as a transition material between the perovskite material and the charge transport material. Since the dissolution of the orthogonal solvent and the perovskite material will cause the performance of the perovskite to decrease, the perovskite solvent dissolves. The charge transport material will lead to the decrease of the charge transport ability of the transport material. No matter which solvent it is, the material will be damaged to varying degrees, which means that for different researchers and different operating methods, the prepared devices and the target performance are very different. , the result is poor device repeatability, high fabrication complexity, and large batch difficulty.

本发明所要解决的技术问题在于,一方面是使得钙钛矿材料和电荷传输材料的有效匹配,具体表现在界面势垒低、电荷输运能力好;另一方面是不引入正交溶剂使电荷传输材料或钙钛矿材料互相溶解,具体表现在避免功能材料之间的互相溶解。采用极性界面作为调控钙钛矿材料及光电器件的手段,可通过两方面来影响最终器件性能,一方面是极性界面能够将性能突出的衬底、电荷传输材料和钙钛矿材料结合到一起,使得各功能材料发挥突出优势最终调控器件性能;另一方面是调控晶体生长过程,通过调控钙钛矿形貌、缺陷态密度等,达到提高或者调控发光性能、光伏性能、载流子注入、载流子传输的目的,最终调控器件整体性能。本发明的目的是提出基于极性界面调控钙钛矿材料及光电器件的方法,能够达到两方面的目的,一方面是界面采用极性材料,能够实现钙钛矿材料和电荷传输材料的有效匹配,其引入的界面材料使得性能优异的电荷传输材料与钙钛矿材料相互兼容,且不会带来性能的降低;另一方面是界面采用极性材料调控钙钛矿的生长,极性界面采用热蒸镀、磁控溅射、MOCVD、ALD、喷涂、印刷、化学合成等物理或化学的方法,沉积到钙钛矿或电荷传输材料上,沉积的材料不会溶解其沉积界面,同时隔绝了电荷传输材料和钙钛矿材料溶剂直接接触,故不会存在电荷传输材料和钙钛矿材料互相溶解的过程,从而将电荷传输材料和钙钛矿材料有效匹配以保证各自的优异特性。The technical problem to be solved by the present invention is that, on the one hand, the effective matching of the perovskite material and the charge transport material is achieved, which is embodied in the low interface barrier and the good charge transport ability; The transport material or perovskite material dissolves in each other, which is embodied in avoiding mutual dissolution between functional materials. The use of polar interfaces as a means of regulating perovskite materials and optoelectronic devices can affect the final device performance through two aspects. At the same time, each functional material can exert its outstanding advantages and ultimately regulate the performance of the device; on the other hand, it is to regulate the crystal growth process. By regulating the morphology of the perovskite, the density of defect states, etc., it can improve or regulate the luminescence performance, photovoltaic performance, and carrier injection. , the purpose of carrier transport, and ultimately control the overall performance of the device. The purpose of the present invention is to propose a method for regulating perovskite materials and optoelectronic devices based on polar interfaces, which can achieve two purposes. , the interface material introduced by it makes the charge transport material with excellent performance and perovskite material compatible with each other, and will not bring about performance degradation; Thermal evaporation, magnetron sputtering, MOCVD, ALD, spraying, printing, chemical synthesis and other physical or chemical methods, deposited on perovskite or charge transport materials, the deposited material will not dissolve its deposition interface, while isolating The charge transport material and the perovskite material are in direct contact with the solvent, so there is no mutual dissolution process of the charge transport material and the perovskite material, so that the charge transport material and the perovskite material are effectively matched to ensure their excellent properties.

图1为普通衬底极性界面的钙钛矿结构,将钙钛矿沉积到覆盖有极性界面的衬底上,其中L1为钙钛矿薄膜,L2为极性界面,L3为衬底(下面以石英片为衬底材料进行描述)。Figure 1 shows the perovskite structure at the polar interface of the common substrate. The perovskite is deposited on the substrate covered with the polar interface, where L1 is the perovskite film, L2 is the polar interface, and L3 is the substrate ( In the following, the quartz plate is used as the substrate material to be described).

石英片衬底L3尺寸为12mm*12mm,石英片在使用前用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇7个步骤进行15分钟超声清洗。清洗完成的石英片放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗,随后将石英片衬底转移到充满高纯氮的手套箱,并转移到真空镀膜机中进行极性界面蒸镀实验。The size of the quartz wafer substrate L3 is 12mm*12mm. The quartz wafer is ultrasonically cleaned with 7 steps of deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, and isopropanol for 15 minutes before use. . The cleaned quartz wafers were placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning, and then the quartz wafer substrates were transferred to a glove box filled with high-purity nitrogen, and then transferred to a vacuum coating machine for polar interface evaporation experiments. .

极性界面L_2分别为NiO、MoO3、ZnO、MgO、Li2CO3、Na2CO3、LiF、CaF2、NaF、KF、CsF、MgO(在具体实施例中进行了这些材料的对比蒸镀实验,这里就全部列出),作为对比的石英片衬底则不蒸镀极性界面。真空蒸镀的气压为5 x 10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.01 nm/s,极性界面蒸镀厚度均为1 nm,蒸镀有极性界面的石英片再转移到充满高纯氮的手套箱旋涂钙钛矿薄膜。The polar interfaces L_2 are NiO, MoO 3 , ZnO, MgO, Li 2 CO 3 , Na 2 CO 3 , LiF, CaF 2 , NaF, KF, CsF, MgO (in the specific examples, the comparative distillation of these materials was carried out). Plating experiments, all listed here), as a comparison quartz wafer substrate does not evaporate the polar interface. The pressure of vacuum evaporation is 5 x 10 -4 Pa, the evaporation rate is measured by a quartz crystal oscillator, the evaporation rate is 0.01 nm/s, the thickness of the polar interface evaporation is 1 nm, and the quartz with polar interface is evaporated The sheets were then transferred to a glove box filled with high purity nitrogen for spin-coated perovskite films.

钙钛矿薄膜L1组分为卤化物钙钛矿,钙钛矿前驱体溶液为PEAnCsPbnBr3n+1,其由110mg的PbBr2(溴化铅)、64mg的CsBr(溴化铯)和24mg的PEABr(2-苯乙基溴化铵)组成,按照摩尔比为1:1:0.4的比例溶解在1mL的DMSO(二甲基亚砜)溶液中,溶液浓度为0.3 mol/L,溶液放置于60℃热台上搅拌1h。旋涂钙钛矿时将蒸镀有极性界面的石英片放到真空旋涂机上,用100uL移液枪吸取30uL的钙钛矿前驱体溶液,滴到蒸镀有极性界面的石英片上,真空旋涂机以3000 rpm/s转速旋涂60 s,接着将旋涂完成钙钛矿的石英片放置到热台上进行60℃退火10 min,得到厚度为35 nm的钙钛矿发光薄膜。The L1 component of the perovskite film is halide perovskite, and the perovskite precursor solution is PEA n CsPb n Br 3n+1 , which consists of 110 mg of PbBr 2 (lead bromide), 64 mg of CsBr (cesium bromide) and 24 mg of PEABr (2-phenethylammonium bromide), dissolved in 1 mL of DMSO (dimethyl sulfoxide) solution at a molar ratio of 1:1:0.4, the solution concentration was 0.3 mol/L, The solution was placed on a 60°C hot stage and stirred for 1 h. When spin-coating perovskite, put the evaporated quartz sheet with polar interface on the vacuum spin coater, suck 30uL of perovskite precursor solution with a 100uL pipette, and drop it onto the evaporated quartz sheet with polar interface, The vacuum spin coater was used for spin coating at 3000 rpm/s for 60 s, and then the perovskite-coated quartz sheet was placed on a hot stage for annealing at 60 °C for 10 min to obtain a perovskite luminescent film with a thickness of 35 nm.

最终钙钛矿薄膜L1、极性界面L2、衬底L3构成发光器件,但此结构是无导电性衬底。Finally, the perovskite thin film L1, the polar interface L2, and the substrate L3 constitute a light-emitting device, but this structure is a non-conductive substrate.

图2为带有ITO的可导电性衬底的极性界面钙钛矿光电器件结构Figure 2 shows the structure of a polar interface perovskite optoelectronic device with a conductive substrate with ITO.

制备基于极性界面的钙钛矿发光器件所选取的衬底为不带ITO(氧化铟锡)的石英片,制备基于极性界面的钙钛矿光电器件所选取的衬底为带ITO(氧化铟锡)的石英片,两种器件结构的制备流程分别如下:The substrate selected for the preparation of the polar interface-based perovskite light-emitting device is a quartz plate without ITO (indium tin oxide), and the substrate selected for the preparation of the polar interface-based perovskite optoelectronic device is a substrate with ITO (oxide). Indium tin) quartz wafer, the preparation process of the two device structures are as follows:

一、 制备基于极性界面的钙钛矿发光器件。1. Preparation of perovskite light-emitting devices based on polar interfaces.

基于极性界面的钙钛矿发光器件所选取的衬底为不带ITO(氧化铟锡)L6的石英片衬底L3,其器件制备过程如下:The substrate selected for the polar interface-based perovskite light-emitting device is a quartz wafer substrate L3 without ITO (indium tin oxide) L6. The device preparation process is as follows:

步骤一,清洗处理不可导电性衬底L3:不可导电性的衬底石英片L3成分为SiO2,尺寸为12mm*12mm,其厚度为1mm。使用前需要对不可导电性衬底L3需要进行前处理,首先用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇七个步骤分别进行15分钟超声清洗,再将衬底放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗。Step 1, cleaning the non-conductive substrate L3: the non-conductive substrate quartz plate L3 is composed of SiO 2 , the size is 12mm*12mm, and the thickness is 1mm. The non-conductive substrate L3 needs to be pre-treated before use. First, use seven steps of deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, and isopropanol for 15 minutes of ultrasound respectively. After cleaning, the substrate was placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning.

步骤二,蒸镀极性界面材料L2:将清洗完成的不可导电性衬底L3放置到玻璃培养皿中,并通过手套箱的过渡仓将玻璃培养皿传送进入带有真空镀膜机的氮气手套箱。打开手套箱内真空镀膜机的仓门,将不可导电性衬底L3从玻璃培养皿中取出,并放置到真空镀膜机中的蒸镀基板台上,调整好蒸镀基板台的位置,关闭基板台下方挡板。Step 2: Evaporate polar interface material L2: place the cleaned non-conductive substrate L3 in a glass petri dish, and transfer the glass petri dish into a nitrogen glove box with a vacuum coater through the transition chamber of the glove box . Open the door of the vacuum coating machine in the glove box, take out the non-conductive substrate L3 from the glass petri dish, and place it on the evaporation substrate stage in the vacuum coating machine, adjust the position of the evaporation substrate stage, and close the substrate Baffle below the table.

将极性界面材料L2传送到真空镀膜机中,放入热蒸发坩埚中,调整好热蒸发坩埚位置,对准放置有不可导电性衬底L3的蒸镀基板台,关闭真空镀膜机的仓门。由于极性界面材料很容易被大气中的水汽、氧气和其它气体影响,导致纯度降低,性能下降,所以极性界面材料L2存储在充满高纯氮的手套箱内,在使用时再将极性界面材料L2传送进入真空镀膜机中。Transfer the polar interface material L2 into the vacuum coating machine, put it into the thermal evaporation crucible, adjust the position of the thermal evaporation crucible, align the evaporation substrate table on which the non-conductive substrate L3 is placed, and close the door of the vacuum coating machine. . Because the polar interface material is easily affected by water vapor, oxygen and other gases in the atmosphere, resulting in a decrease in purity and performance, the polar interface material L2 is stored in a glove box filled with high-purity nitrogen, and the polar interface material L2 is stored in a glove box filled with high-purity nitrogen. The interface material L2 is conveyed into the vacuum coater.

基板台下方挡板是为了阻挡极性界面材料直接蒸镀到不可导电性衬底L3上,由于在蒸镀过程中,材料的蒸发速率和材料纯度对制备的极性界面薄膜L2影响很大,所以需要等待真空镀膜机内石英晶振片检测的速率稳定后才能够打开基板台下方挡板,蒸发速率稳定的极性界面材料L2可以均匀蒸镀到不可导电性衬底L3上。The baffle below the substrate stage is to prevent the polar interface material from being directly evaporated on the non-conductive substrate L3. During the evaporation process, the evaporation rate and material purity of the material have a great influence on the prepared polar interface film L2. Therefore, it is necessary to wait for the detection rate of the quartz crystal in the vacuum coating machine to stabilize before opening the baffle below the substrate stage. The polar interface material L2 with a stable evaporation rate can be uniformly evaporated onto the non-conductive substrate L3.

开启连接真空镀膜机的机械泵、分子泵后,等待真空蒸镀的气压下降为5 x 10-4 Pa,开启热蒸发坩埚的电源,热蒸发坩埚的电源对热蒸发坩埚逐渐加热,防止加载到热蒸发坩埚的热过快,导致极性界面材料L2的喷溅,对热蒸发坩埚进行逐渐加热有助于形成均匀蒸发的极性界面材料L2蒸发速率,故需要对热蒸发坩埚逐渐加热。After turning on the mechanical pump and molecular pump connected to the vacuum coating machine, wait for the pressure of vacuum evaporation to drop to 5 x 10 -4 Pa, then turn on the power supply of the thermal evaporation crucible, and the power supply of the thermal evaporation crucible will gradually heat the thermal evaporation crucible to prevent loading into the thermal evaporation crucible. The heating of the thermal evaporation crucible is too fast, resulting in the splash of the polar interface material L2. Gradual heating of the thermal evaporation crucible helps to form a uniform evaporation rate of the polar interface material L2, so it is necessary to gradually heat the thermal evaporation crucible.

通过膜厚仪显示出石英晶振片所检测的极性界面材料L2的蒸发速率,等待膜厚仪显示的极性界面材料L2的蒸发速率稳定后,蒸镀速率稳定在0.01nm/s,开启真空镀膜机中基板台下方的挡板,蒸发速率均匀的极性界面材料L2可均匀蒸镀到不可导电性衬底L3上,极性界面蒸镀厚度为1nm。The evaporation rate of the polar interface material L2 detected by the quartz crystal oscillator is displayed by the film thickness meter. After the evaporation rate of the polar interface material L2 displayed by the film thickness meter is stabilized, the evaporation rate is stabilized at 0.01nm/s, and the vacuum is turned on. In the baffle plate below the substrate stage in the coating machine, the polar interface material L2 with uniform evaporation rate can be uniformly evaporated onto the non-conductive substrate L3, and the polar interface evaporation thickness is 1 nm.

蒸镀完极性界面材料L2后,关闭真空镀膜机中基板台下方的挡板,关闭连接真空镀膜机的分子泵、机械泵,然后等待真空镀膜机内气压恢复至大气压,打开真空镀膜机的仓门,从基板台上取出蒸镀有极性界面材料L2的不可导电性衬底L3。然后将其放置到玻璃培养皿中,将玻璃培养皿通过过渡仓传送至有真空旋涂机的手套箱,接下来旋涂卤化物钙钛矿薄膜L1。After evaporating the polar interface material L2, close the baffle plate below the substrate stage in the vacuum coating machine, close the molecular pump and mechanical pump connected to the vacuum coating machine, and then wait for the pressure in the vacuum coating machine to return to atmospheric pressure, and turn on the vacuum coating machine. The door is opened, and the non-conductive substrate L3 on which the polar interface material L2 is vapor-deposited is taken out from the substrate stage. It was then placed into a glass petri dish, which was transferred through a transition chamber to a glove box with a vacuum spin coater, followed by spin coating of the halide perovskite thin film L1.

步骤三,旋涂卤化物钙钛矿L1:蒸镀有极性界面材料L2的不可导电性衬底L3再通过玻璃培养皿转移到有真空旋涂机的手套箱旋涂卤化物钙钛矿薄膜,旋涂钙钛矿时将蒸镀有极性界面的衬底放到真空旋涂机上,用移液枪吸取钙钛矿前驱体溶液,滴到蒸镀有极性界面的衬底上,真空旋涂机以3000 rpm/s转速旋涂60 s,接着将旋涂完成钙钛矿的衬底放置到热台上进行60 ℃退火10 min,得到钙钛矿薄膜器件。Step 3, spin coating halide perovskite L1: the non-conductive substrate L3 with polar interface material L2 is evaporated and then transferred to a glove box with a vacuum spin coater through a glass petri dish to spin a halide perovskite film , when spin coating perovskite, put the substrate with polar interface on the vacuum spin coater, suck the perovskite precursor solution with a pipette, drop it on the substrate with polar interface, vacuum The spin-coater spins at 3000 rpm/s for 60 s, and then the spin-coated perovskite substrate is placed on a hot stage for annealing at 60 °C for 10 min to obtain a perovskite thin film device.

最终形成基于极性界面的卤化物钙钛矿发光器件,用高于卤化物钙钛矿发光能量的激发光去激发卤化物钙钛矿发光薄膜,卤化物钙钛矿可发出荧光,基于此方法可制备也可用于基于柔性衬底的荧光薄膜。Finally, a halide perovskite light-emitting device based on a polar interface is formed. The halide perovskite light-emitting film is excited by excitation light higher than the luminescence energy of the halide perovskite, and the halide perovskite can emit fluorescence. Based on this method Fluorescent films can also be prepared that can also be used on flexible substrates.

二、制备基于极性界面的钙钛矿光电器件。2. Preparation of perovskite optoelectronic devices based on polar interfaces.

基于极性界面的钙钛矿光电器件所选取的衬底为带ITO(氧化铟锡)L6的石英片,制备流程留下:The substrate selected for the polar interface-based perovskite optoelectronic device is a quartz sheet with ITO (indium tin oxide) L6, and the preparation process leaves:

步骤一,制备带有ITO(氧化铟锡)L6的可导电性衬底:可导电性的衬底由ITO(氧化铟锡)L6和石英片衬底L3构成,石英片成分为SiO2,尺寸为12mm*12mm,其厚度为1mm。ITO可通过磁控溅射技术将ITO原料溅射到石英片上,ITO厚度为185nm,溅射ITO(氧化铟锡)L6时,将石英片衬底L3放置到有掩膜版的基板台上,可用掩膜版对石英片衬底L3进行部分遮挡,暴露出来部分可以溅射上ITO材料,未暴露出来部分不能够溅射上ITO材料,通过掩膜版实现在石英片衬底L3上居中溅射出8*12mm的长方形ITO(氧化铟锡)L6的形状,每边空余2mm空白位置,空白位置没有ITO覆盖。Step 1, prepare a conductive substrate with ITO (indium tin oxide) L6: the conductive substrate is composed of ITO (indium tin oxide) L6 and a quartz wafer substrate L3, the composition of the quartz wafer is SiO 2 , and the size It is 12mm*12mm, and its thickness is 1mm. ITO can sputter the ITO raw material onto the quartz wafer by the magnetron sputtering technology. The thickness of ITO is 185nm. When sputtering ITO (indium tin oxide) L6, the quartz wafer substrate L3 is placed on the substrate stage with the mask. The quartz wafer substrate L3 can be partially shielded by a mask. The exposed part can be sputtered with ITO material, and the unexposed part cannot be sputtered with ITO material. The mask can be used to achieve center sputtering on the quartz wafer substrate L3. The shape of 8*12mm rectangular ITO (indium tin oxide) L6 is shot, with 2mm blank space on each side, and the blank position is not covered by ITO.

步骤二,可导电性衬底的清洗处理:对于可导电性衬底需要进行前处理,首先用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇七个步骤分别进行15分钟超声清洗,再将可导电性衬底放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗。Step 2, the cleaning treatment of the conductive substrate: the conductive substrate needs to be pre-treated, firstly use deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, isopropanol The seven steps were ultrasonically cleaned for 15 minutes respectively, and then the conductive substrate was placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning.

步骤三,制备电荷传输材料L7薄膜:将清洗完成的可导电性衬底放置到玻璃培养皿中,并通过手套箱的过渡仓将玻璃培养皿传送进入氮气手套箱,然后将可导电性衬底放到氮气手套箱内的真空旋涂机上。电荷传输材料L7是溶解在溶剂中,用100uL移液枪吸取30uL电荷传输材料溶液均匀涂覆到可导电性的衬底上,电荷传输材料L7可以将ITO(氧化铟锡)L6全部包覆起来,开启真空旋涂机按钮以3000rpm转速旋涂60s,形成电荷传输材料L7的薄膜,电荷传输材料L7薄膜旋涂完成后,将覆盖有电荷传输材料L7的可导电性衬底放置到热台上进行120℃高温退火,时间为10min,最终在可导电性衬底上形成包覆ITO(氧化铟锡)L6的电荷传输材料薄膜L7。Step 3: Prepare the charge transport material L7 film: place the cleaned conductive substrate into a glass petri dish, and transfer the glass petri dish into the nitrogen glove box through the transition chamber of the glove box, and then transfer the conductive substrate to the glass petri dish. Placed on a vacuum spin coater in a nitrogen glove box. The charge transport material L7 is dissolved in the solvent, and 30uL of the charge transport material solution is drawn with a 100uL pipette and evenly coated on the conductive substrate. The charge transport material L7 can completely coat the ITO (indium tin oxide) L6. , turn on the vacuum spin coater button and spin at 3000rpm for 60s to form a thin film of the charge transport material L7. After the spin coating of the charge transport material L7 film is completed, place the conductive substrate covered with the charge transport material L7 on the hot stage. A high temperature annealing at 120°C is performed for 10 min, and finally a charge transport material film L7 coated with ITO (indium tin oxide) L6 is formed on the conductive substrate.

步骤四,蒸镀极性界面材料L2:打开手套箱内真空镀膜机的仓门,将从热台上取下的制备有电荷传输材料L7的可导电性衬底放置到玻璃培养皿中,通过过渡仓传送进入带有真空镀膜机的手套箱中,制备有电荷传输材料L7的可导电性衬底取出,放置到真空镀膜机中的蒸镀基板台上,调整好蒸镀基板台的位置,关闭基板台下方挡板。Step 4: Evaporating the polar interface material L2: Open the door of the vacuum coating machine in the glove box, place the conductive substrate prepared with the charge transport material L7 removed from the hot stage into a glass petri dish, and pass The transition bin is transferred into the glove box with the vacuum coating machine, and the conductive substrate prepared with the charge transport material L7 is taken out, placed on the evaporation substrate stage in the vacuum coating machine, and the position of the evaporation substrate stage is adjusted. Close the shutter under the substrate stage.

将极性界面材料L2也传送到真空镀膜机中,放入热蒸发坩埚中,调整好热蒸发坩埚位置,对准放置有电荷传输材料L7的可导电性衬底的蒸镀基板台,关闭真空镀膜机的仓门。由于极性界面材料很容易被大气中的水汽、氧气和其它气体影响,导致纯度降低,性能下降,所以极性界面材料存储在充满高纯氮的手套箱内,在使用时再将材料传送进入真空镀膜机中。Transfer the polar interface material L2 into the vacuum coating machine, put it into the thermal evaporation crucible, adjust the position of the thermal evaporation crucible, align the evaporation substrate stage with the conductive substrate on which the charge transport material L7 is placed, and turn off the vacuum The door of the coating machine. Since the polar interface material is easily affected by water vapor, oxygen and other gases in the atmosphere, resulting in a decrease in purity and performance, the polar interface material is stored in a glove box filled with high-purity nitrogen, and the material is transferred into the in the vacuum coating machine.

基板台下方挡板是为了阻挡极性界面材料L2直接蒸镀到制备有电荷传输材料L7的可导电性衬底上,由于在蒸镀过程中,材料的蒸发速率和材料纯度对制备的极性界面材料L2影响很大,所以需要等待真空镀膜机内石英晶振片检测的速率稳定后才能够打开基板台下方挡板,蒸发速率稳定的极性界面材料L2可以均匀蒸镀到覆盖有电荷传输材料L7的可导电性衬底上。The baffle below the substrate stage is to prevent the polar interface material L2 from being directly evaporated on the conductive substrate prepared with the charge transport material L7, because during the evaporation process, the evaporation rate and material purity of the material have an impact on the polarity of the preparation. The interface material L2 has a great influence, so it is necessary to wait for the detection rate of the quartz crystal oscillator in the vacuum coating machine to stabilize before opening the baffle under the substrate stage. The polar interface material L2 with a stable evaporation rate can be uniformly evaporated to cover the charge transport material. on the conductive substrate of L7.

开启连接真空镀膜机的机械泵、分子泵后,等待真空蒸镀的气压下降为5 x 10-4 Pa,开启热蒸发坩埚的电源,热蒸发坩埚的电源对热蒸发坩埚逐渐加热,防止加载到热蒸发坩埚的热过快,导致极性界面材料L2的喷溅,对热蒸发坩埚进行逐渐加热有助于形成均匀蒸发的极性界面材料L2蒸发速率,故需要对热蒸发坩埚逐渐加热。After turning on the mechanical pump and molecular pump connected to the vacuum coating machine, wait for the pressure of vacuum evaporation to drop to 5 x 10 -4 Pa, then turn on the power supply of the thermal evaporation crucible, and the power supply of the thermal evaporation crucible will gradually heat the thermal evaporation crucible to prevent loading into the thermal evaporation crucible. The heating of the thermal evaporation crucible is too fast, resulting in the splash of the polar interface material L2. Gradual heating of the thermal evaporation crucible helps to form a uniform evaporation rate of the polar interface material L2, so it is necessary to gradually heat the thermal evaporation crucible.

通过膜厚仪显示出石英晶振片所检测的极性界面材料L2的蒸发速率,等待膜厚仪显示的极性界面材料L2的蒸发速率稳定后,蒸镀速率稳定在0.01nm/s,开启真空镀膜机中基板台下方的挡板,蒸发速率均匀的极性界面材料L2可以均匀沉积到覆盖有电荷传输材料L7的可导电性衬底上,极性界面蒸镀厚度为1nm,最终形成极性界面材料薄膜L2。The evaporation rate of the polar interface material L2 detected by the quartz crystal oscillator is displayed by the film thickness meter. After the evaporation rate of the polar interface material L2 displayed by the film thickness meter is stabilized, the evaporation rate is stabilized at 0.01nm/s, and the vacuum is turned on. The baffle plate under the substrate stage in the coating machine, the polar interface material L2 with uniform evaporation rate can be uniformly deposited on the conductive substrate covered with the charge transport material L7, and the polar interface evaporation thickness is 1nm, and finally the polar interface material is formed. Interface material film L2.

蒸镀完极性界面材料L2后,关闭真空镀膜机中基板台下方的挡板,关闭连接真空镀膜机的分子泵、机械泵,然后等待真空镀膜机内气压恢复至大气压,打开真空镀膜机的仓门,从基板台上取出蒸镀有极性界面材料L2,覆盖有电荷传输材料L7的可导电性衬底。然后将其放置到玻璃培养皿中,将培养皿通过过渡仓传送至有真空旋涂机的手套箱。After evaporating the polar interface material L2, close the baffle plate below the substrate stage in the vacuum coating machine, close the molecular pump and mechanical pump connected to the vacuum coating machine, and then wait for the pressure in the vacuum coating machine to return to atmospheric pressure, and turn on the vacuum coating machine. The chamber door is removed from the substrate stage, and the conductive substrate on which the polar interface material L2 is vapor-deposited and covered with the charge transport material L7 is taken out. It was then placed into a glass petri dish, which was transferred through a transition chamber to a glove box with a vacuum spin coater.

步骤五,旋涂卤化物钙钛矿薄膜L1:钙钛矿薄膜为卤化物钙钛矿,卤化物钙钛矿由不同组分构成,溶解在极性溶剂中可形成不同特性的前驱体溶液。旋涂时将蒸镀有极性界面材料L2、覆盖有电荷传输材料L7的可导电性衬底放置到真空旋涂机上,用100uL移液枪吸取30uL的卤化物钙钛矿前驱体溶液均匀涂覆到蒸镀有极性界面材料L2、覆盖有电荷传输材料L7的可导电性衬底上,开启真空旋涂机的按钮以5000rpm转速旋涂60s,形成卤化物钙钛矿L1的薄膜,将覆盖有卤化物钙钛矿L1、蒸镀有极性界面材料L2、覆盖有电荷传输材料L7的可导电性衬底放置到热台上进行90℃高温退火,时间为10min,最终形成均匀的卤化物钙钛矿薄膜L1。Step 5, spin coating the halide perovskite thin film L1: the perovskite thin film is a halide perovskite, and the halide perovskite is composed of different components, which can be dissolved in a polar solvent to form a precursor solution with different characteristics. During spin coating, the conductive substrate evaporated with polar interface material L2 and covered with charge transport material L7 is placed on a vacuum spin coater, and 30uL of halide perovskite precursor solution is drawn with a 100uL pipette to evenly coat it. Coated on the conductive substrate evaporated with polar interface material L2 and covered with charge transport material L7, turned on the button of the vacuum spin coater and spin-coated at 5000 rpm for 60 s to form a thin film of halide perovskite L1. The conductive substrate covered with halide perovskite L1, evaporated with polar interface material L2, and covered with charge transport material L7 was placed on a hot stage for annealing at a high temperature of 90 °C for 10 min, and a uniform halogenation was finally formed. material perovskite thin film L1.

步骤六,蒸镀阴极电荷传输材料L5:将退火完成的覆盖有卤化物钙钛矿L1、蒸镀有极性界面材料L2、覆盖有电荷传输材料L7的可导电性衬底放到玻璃培养皿中,并通过过渡仓传送进入带有真空镀膜机的手套箱中,将其由玻璃培养皿取出放置到真空镀膜机中的蒸镀基板台上,调整好蒸镀基板台的位置,关闭基板台下方挡板。Step 6: Evaporate cathode charge transport material L5: place the annealed conductive substrate covered with halide perovskite L1, evaporated with polar interface material L2, and covered with charge transport material L7 into a glass petri dish , and transfer it into the glove box with the vacuum coating machine through the transition bin, take it out from the glass petri dish and place it on the evaporation substrate stage in the vacuum coating machine, adjust the position of the evaporation substrate stage, and close the substrate stage. Bottom bezel.

将电荷传输材料L5传送到真空镀膜机中,放入热蒸发坩埚中,调整好热蒸发坩埚位置,对准覆盖有卤化物钙钛矿L1、蒸镀有极性界面材料L2、覆盖有电荷传输材料L7的可导电性衬底,关闭真空镀膜机的仓门。由于电荷传输材料很容易被大气中的水汽、氧气和其它气体影响,导致纯度降低,性能下降,所以电荷传输材料L5存储在充满高纯氮的手套箱内,在使用时再将材料传送进入真空镀膜机中。Transfer the charge transport material L5 into the vacuum coating machine, put it into the thermal evaporation crucible, adjust the position of the thermal evaporation crucible, and align the L1 covered with halide perovskite, evaporated with polar interface material L2, and covered with charge transport. The conductive substrate of material L7, close the door of the vacuum coater. Since the charge transport material is easily affected by water vapor, oxygen and other gases in the atmosphere, resulting in a decrease in purity and performance, the charge transport material L5 is stored in a glove box filled with high-purity nitrogen, and then transferred into a vacuum when used. in the coating machine.

开启连接真空镀膜机的机械泵、分子泵后,等待真空蒸镀的气压下降为5 x 10-4 Pa,开启热蒸发坩埚的电源,热蒸发坩埚的电源对热蒸发坩埚逐渐加热,防止加载到热蒸发坩埚的热过快,导致电荷传输材料L5的喷溅,对热蒸发坩埚进行逐渐加热有助于形成均匀蒸发的电荷传输材料L5蒸发速率,故需要对热蒸发坩埚逐渐加热。After turning on the mechanical pump and molecular pump connected to the vacuum coating machine, wait for the pressure of vacuum evaporation to drop to 5 x 10 -4 Pa, then turn on the power supply of the thermal evaporation crucible, and the power supply of the thermal evaporation crucible will gradually heat the thermal evaporation crucible to prevent loading into the thermal evaporation crucible. The heating of the thermal evaporation crucible is too fast, resulting in the sputtering of the charge transport material L5. Gradual heating of the thermal evaporation crucible helps to form a uniform evaporation rate of the charge transport material L5, so it is necessary to gradually heat the thermal evaporation crucible.

通过膜厚仪显示出石英晶振片所检测的电荷传输材料L5的蒸发速率,等待膜厚仪显示的电荷传输材料L5的蒸发速率稳定后,蒸镀速率稳定在0.05nm/s,开启真空镀膜机中基板台下方的挡板,蒸发速率均匀的电荷传输材料L5可以均匀沉积到覆盖有卤化物钙钛矿L1、蒸镀有极性界面材料L2、覆盖有电荷传输材料L7的可导电性衬底上,电荷传输材料L5蒸镀厚度为40nm,最终形成电荷传输材料L5薄膜。The evaporation rate of the charge transport material L5 detected by the quartz crystal oscillator is displayed by the film thickness meter. After the evaporation rate of the charge transport material L5 displayed by the film thickness meter is stabilized, the evaporation rate is stabilized at 0.05nm/s, and the vacuum coating machine is turned on. The baffle below the middle substrate stage, the charge transport material L5 with uniform evaporation rate can be uniformly deposited on the conductive substrate covered with halide perovskite L1, evaporated with polar interface material L2, and covered with charge transport material L7 On the above, the charge transport material L5 is evaporated to a thickness of 40 nm, and finally a thin film of the charge transport material L5 is formed.

步骤七,蒸镀电极L4:蒸镀完成电荷传输材料L5后,在真空镀膜机内将其放置到金属掩膜版上,通过掩膜版的两列长方形形状(1.5mm*3.5mm)L4可形成卤化物钙钛矿薄膜面积为5.25mm2,电极材料由不同种类金属和氟化物构成。Step 7: Evaporate the electrode L4: After the charge transport material L5 is evaporated, it is placed on the metal mask in the vacuum coating machine. The area of the formed halide perovskite film is 5.25 mm 2 , and the electrode materials are composed of different kinds of metals and fluorides.

通过膜厚仪显示出石英晶振片所检测的电极L4的蒸发速率,等待膜厚仪显示的电极L4的蒸发速率稳定后,蒸镀速率稳定在0.2nm/s,开启真空镀膜机中基板台下方的挡板,蒸发速率均匀的电极L4可以均匀沉积到覆盖有电荷传输材料L5、卤化物钙钛矿L1、蒸镀有极性界面材料L2、覆盖有电荷传输材料L7的可导电性衬底上,电极L4蒸镀厚度为100nm,最终形成电极L4薄膜。The evaporation rate of the electrode L4 detected by the quartz crystal oscillator is displayed by the film thickness meter. After the evaporation rate of the electrode L4 displayed by the film thickness meter is stabilized, the evaporation rate is stabilized at 0.2 nm/s, and the vacuum coating machine is turned on under the substrate stage. The baffle plate, the electrode L4 with uniform evaporation rate can be uniformly deposited on the conductive substrate covered with charge transport material L5, halide perovskite L1, evaporated with polar interface material L2, and covered with charge transport material L7. , the electrode L4 is vapor-deposited to a thickness of 100 nm, and finally a thin film of the electrode L4 is formed.

最终形成基于极性界面的卤化物钙钛矿光电器件,通过在ITO(氧化铟锡)L6上和电极L4上加载正、负电压,最终可以实现器件在电流驱动下工作。Finally, a halide perovskite optoelectronic device based on a polar interface is formed. By loading positive and negative voltages on ITO (indium tin oxide) L6 and electrode L4, the device can finally work under current driving.

极性材料的界面采用不同方法形成,例如热蒸镀、磁控溅射、MOCVD、ALD、喷涂、印刷、化学合成等物理或化学的方法,典型沉积厚度范围为0.1 nm ~ 1000 nm,对于目前多数功能材料为纳米级别的器件,可满足当前光电器件的功能需求。The interface of polar materials is formed by different methods, such as thermal evaporation, magnetron sputtering, MOCVD, ALD, spraying, printing, chemical synthesis and other physical or chemical methods. The typical deposition thickness ranges from 0.1 nm to 1000 nm. Most functional materials are nanoscale devices, which can meet the functional requirements of current optoelectronic devices.

相比于直接沉积到石英或玻璃(SiO2)、ITO、Si、FTO、PTFE等衬底上的钙钛矿薄膜缺陷多、晶体取向性差,沉积到极性界面上缺陷少、薄膜覆盖性高,能够实现衬底或传输材料和钙钛矿的有效过渡,极性界面起到调控晶体生长的过程,可调控晶体生长形貌、调控结晶质量、调控发光效率。Compared with the perovskite films deposited directly on quartz or glass (SiO 2 ), ITO, Si, FTO, PTFE and other substrates, there are many defects and poor crystal orientation, while those deposited on polar interfaces have fewer defects and higher film coverage. , which can realize the effective transition between the substrate or the transport material and the perovskite, and the polar interface plays the role of regulating the crystal growth process, which can control the crystal growth morphology, the crystal quality, and the luminous efficiency.

对于元素周期表中不同族元素形成的化合物,对于材料电负性之差在0- 2之间的材料界面为极性材料,对于材料电负性之差大于2的为强极性材料,其形成的材料界面均可起到调控钙钛矿材料及光电器件性能的作用,例如调控钙钛矿晶体生长尺寸、发光波长、光致外量子效率PLQE、太阳能电池的开路电压V OC 、短路电流J SC 、功率转化效率PCE等参数。其材料界面可由多种化合物构成,例如不同周期间可形成化合物的极性材料界面,如ZrO2、V2O5、Al2O3、NiO、MoO3、ZnO、MgO、NiO、SnO2等金属氧化物材料界面。不同族间可形成化合物的极性材料界面,例如Li2CO3、Na2CO3、 Cs2CO3等碳酸根金属化合物材料。不同族间可形成化合物的强极性材料界面,例如LiF、NaF、KF、RbF、CsF、MgF2、CaF2等金属氟化物材料界面。包括其它可以与钙钛矿材料相互配合的材料界面,例如PTFE、压电薄膜、压电陶瓷等材料界面。For compounds formed by elements of different groups in the periodic table, the material interface with the difference in electronegativity of the material between 0 and 2 is a polar material, and for the material with a difference in electronegativity greater than 2, it is a strongly polar material. The formed material interface can play a role in regulating the performance of perovskite materials and optoelectronic devices, such as regulating the growth size of perovskite crystals, luminescence wavelength, photoinduced external quantum efficiency PLQE , solar cell open-circuit voltage V OC , short-circuit current J SC , power conversion efficiency PCE and other parameters. The material interface can be composed of a variety of compounds, such as polar material interfaces that can form compounds during different periods, such as ZrO 2 , V 2 O 5 , Al 2 O 3 , NiO, MoO 3 , ZnO, MgO, NiO, SnO 2 , etc. Metal oxide material interface. The polar material interface of compounds can be formed between different groups, such as Li 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 and other carbonate metal compound materials. Strongly polar material interfaces of compounds can be formed between different groups, such as LiF, NaF, KF, RbF, CsF, MgF 2 , CaF 2 and other metal fluoride material interfaces. Including other material interfaces that can cooperate with perovskite materials, such as PTFE, piezoelectric films, piezoelectric ceramics and other material interfaces.

可通过调控改变材料界面的极性,如调控极性界面为非极性界面,或调控非极性界面为极性界面,最终通过改变材料界面极性方式进而调控器件最终性能。The polarity of the material interface can be changed by adjusting, such as adjusting the polar interface to a non-polar interface, or adjusting the non-polar interface to a polar interface, and finally adjusting the final performance of the device by changing the polarity of the material interface.

极性界面可调控钙钛矿材料发光特性,减少衬底或传输材料对钙钛矿薄膜的荧光淬灭,可调控薄膜荧光寿命和光致外量子效率PLQE。The polar interface can regulate the luminescence properties of perovskite materials, reduce the fluorescence quenching of perovskite films by substrates or transport materials, and can control the fluorescence lifetime and photoinduced external quantum efficiency PLQE of the films.

极性界面可使得钙钛矿材料和电荷传输材料有效匹配,基于极性界面制备的光电器件,其界面会调控各个功能材料之间的注入势垒,调控或增加电荷传输能力,无论在PN型材料还是PIN型材料中,均不会限制载流子的流动,可提高或调控载流子传输特性。The polar interface can effectively match the perovskite material and the charge transport material. For optoelectronic devices prepared based on the polar interface, the interface can regulate the injection barrier between various functional materials, and regulate or increase the charge transport capability, no matter in the PN type. Neither the material nor the PIN-type material restricts the flow of carriers, and can improve or regulate the carrier transport characteristics.

极性界面的引入可平衡电子空穴的传输速率,调控钙钛矿光电子器件的性能,例如降低发光二极管的开启电压V T 、提高发光亮度,提高太阳能电池的填充因子FF、开路电压V OC 、短路电流J SC 、功率转化效率PCE等参数,增加光电探测器的探测灵敏度等。The introduction of polar interfaces can balance the transport rate of electrons and holes, and regulate the performance of perovskite optoelectronic devices, such as reducing the turn - on voltage VT of light-emitting diodes, improving luminous brightness, and improving the fill factor FF , open-circuit voltage V OC , Short-circuit current J SC , power conversion efficiency PCE and other parameters, increase the detection sensitivity of the photodetector, etc.

极性材料界面可以应用于多种光电器件方面,包括太阳能电池、发光二极管、探测器、荧光薄膜、荧光粉、半导体晶体管、激光等光电子器件和材料方面。Polar material interfaces can be applied to a variety of optoelectronic devices, including solar cells, light-emitting diodes, detectors, fluorescent films, phosphors, semiconductor transistors, lasers and other optoelectronic devices and materials.

工作原理working principle

目前钙钛矿材料及光电器件在光电性能和稳定性方面仍存在不足,因为钙钛矿属于极性离子晶体,根据相似相容原理,如果存在晶格不匹配的现象,会带来多方面问题。主要原因表现为两方面,一方面是性能突出的衬底、电荷传输材料和钙钛矿材料不能完美匹配,限制了制备的钙钛矿光电器件的性能,例如对于溶液法制备的光电器件,电荷传输材料、钙钛矿材料存在界面互溶现象,导致界面不完美进而影响到各功能材料的性能;另一方面是钙钛矿材料存在问题,表现为晶体生长质量差、晶界及界面缺陷多,最终限制钙钛矿材料及光电器件的性能,目前在制备过程中可采用多种方法调控钙钛矿结晶质量,最终提高或调控钙钛矿材料及光电器件的性能。基于这两方面的问题,在优化钙钛矿材料及光电器件时需要考虑不引入新的成分破坏原来钙钛矿组分,同时也需要使得钙钛矿材料和电荷传输材料有效匹配。本发明中采用极性界面作为调控钙钛矿材料及光电器件的手段,可通过两方面来影响最终器件性能,一方面是极性界面能够将性能突出的衬底、电荷传输材料和钙钛矿材料结合到一起,使得各功能材料发挥作用最终调控器件性能;另一方面是调控晶体生长过程,通过调控钙钛矿形貌、缺陷态密度等,达到提高或者调控发光性能、光伏性能、载流子注入、载流子传输的目的,最终优化或调控器件整体性能。At present, perovskite materials and optoelectronic devices are still insufficient in terms of optoelectronic properties and stability, because perovskites are polar ionic crystals. According to the principle of similarity compatibility, if there is a phenomenon of lattice mismatch, it will bring many problems. . The main reasons are two aspects. On the one hand, the outstanding performance of substrates, charge transport materials and perovskite materials cannot be perfectly matched, which limits the performance of the prepared perovskite optoelectronic devices. For example, for optoelectronic devices prepared by solution methods, the charge Transport materials and perovskite materials have interfacial dissolution phenomenon, which leads to imperfect interface and affects the performance of various functional materials; on the other hand, perovskite materials have problems, which are manifested in poor crystal growth quality, many grain boundaries and interface defects The performance of perovskite materials and optoelectronic devices is ultimately limited. At present, various methods can be used to control the crystal quality of perovskite in the preparation process, and ultimately improve or regulate the performance of perovskite materials and optoelectronic devices. Based on these two issues, when optimizing perovskite materials and optoelectronic devices, it is necessary to consider not to introduce new components to destroy the original perovskite components, and at the same time, it is also necessary to effectively match perovskite materials and charge transport materials. In the present invention, the polar interface is used as a means of regulating perovskite materials and optoelectronic devices, which can affect the performance of the final device through two aspects. The combination of materials makes each functional material play a role in ultimately regulating the performance of the device; on the other hand, it regulates the crystal growth process. By regulating the morphology of the perovskite, the density of defect states, etc., the luminescence performance, photovoltaic performance, current carrying performance, etc. can be improved or regulated. The purpose of sub-injection and carrier transport is to ultimately optimize or regulate the overall performance of the device.

例如采用强极性材料作为钙钛矿器件的界面材料,由于钙钛矿是强极性材料,钙钛矿可以和极性材料很好的配合,故选取一些不同的极性材料作为界面材料引入到电荷传输材料和钙钛矿材料之间进行晶格匹配。通过采用超薄的极性材料沉积到聚合物空穴传输材料上,可保证钙钛矿有效生长到覆盖有极性界面的聚合物电荷传输材料上,且采用强极性材料可以增加钙钛矿晶体生长的质量,表现为增加钙钛矿薄膜的载流子寿命、增加钙钛矿薄膜的外量子效率PLQE,进而增加薄膜的稳定性和基于钙钛矿的器件性能。For example, strong polar materials are used as interface materials of perovskite devices. Since perovskites are strong polar materials, perovskites can cooperate well with polar materials, so some different polar materials are selected as interface materials to introduce Lattice matching between charge transport materials and perovskite materials. By depositing ultrathin polar materials on polymer hole transport materials, the perovskite can be effectively grown on the polymer charge transport materials covered with polar interfaces, and the use of strong polar materials can increase the perovskite The quality of crystal growth is manifested in increasing the carrier lifetime of the perovskite film, increasing the external quantum efficiency PLQE of the perovskite film, and thus increasing the film stability and perovskite-based device performance.

极性界面采用热蒸镀、磁控溅射、MOCVD、ALD、喷涂、印刷、化学合成等物理或化学的方法,沉积到钙钛矿或电荷传输材料上,典型沉积厚度范围为0.1 nm ~ 1000nm,对于目前多数功能材料为纳米级别的器件,可满足当前大部分光电器件的功能需求。相比于直接沉积到SiO2衬底上的钙钛矿薄膜缺陷多、晶体取向性差,极性界面起到调控晶体生长的作用,极性界面与极性钙钛矿相匹配可增加薄膜质量,可增加晶体钙钛矿生长尺寸、减少面缺陷和体缺陷密度,且不会影响薄膜本身的光谱特性及组分,使得钙钛矿薄膜可有效抑制非辐射复合、增加辐射复合,进而增加薄膜载流子荧光寿命,实现更高光致外量子效率。极性界面由于隔绝电荷传输材料和钙钛矿材料,可减少衬底或传输材料对钙钛矿薄膜的荧光淬灭。The polar interface is deposited on the perovskite or charge transport material by physical or chemical methods such as thermal evaporation, magnetron sputtering, MOCVD, ALD, spraying, printing, chemical synthesis, and the typical deposition thickness ranges from 0.1 nm to 1000 nm. , for most of the current functional materials are nanoscale devices, which can meet the functional requirements of most of the current optoelectronic devices. Compared with the perovskite film deposited directly on the SiO2 substrate, there are many defects and poor crystal orientation, and the polar interface plays a role in regulating the crystal growth. The matching of the polar interface with the polar perovskite can increase the film quality. It can increase the growth size of crystalline perovskite, reduce the density of surface defects and bulk defects, and will not affect the spectral characteristics and components of the film itself, so that the perovskite film can effectively inhibit non-radiative recombination, increase radiative recombination, and then increase the film loading. The lifetime of the carrier fluorescence is higher, and the higher photo-induced external quantum efficiency is achieved. The polar interface can reduce the fluorescence quenching of the perovskite film by the substrate or the transport material due to the isolation of the charge transport material and the perovskite material.

极性界面可使得钙钛矿材料和电荷传输材料有效匹配,基于极性界面制备的光电器件,其界面会调控电荷传输材料和钙钛矿材料间注入势垒,调控或增加电荷传输能力。极性界面作为非常薄的隧穿材料,无论在PN型材料还是PIN型材料中,均不会限制载流子的流动。如果利用较厚的极性界面材料,可以利用其双极性特性,对空穴或电子部分阻挡以实现器件中电荷平衡,实现传输电荷调控以平衡电子空穴的传输速率,可提高钙钛矿光电子器件的性能,例如降低发光二极管的开启电压V T 、提高太阳能电池的填充因子FF、短路电流J SC 、开路电压V OC 、功率转化效率PCE、增加光电探测器的探测灵敏度等参数。The polar interface can effectively match the perovskite material and the charge transport material. In optoelectronic devices prepared based on the polar interface, the interface can regulate the injection barrier between the charge transport material and the perovskite material, and regulate or increase the charge transport capability. As a very thin tunneling material, the polar interface will not restrict the flow of carriers in either PN-type or PIN-type materials. If a thicker polar interface material is used, its bipolar properties can be used to partially block holes or electrons to achieve charge balance in the device, and to achieve charge transfer regulation to balance the electron-hole transport rate, which can improve perovskite. The performance of optoelectronic devices, such as reducing the turn - on voltage VT of light-emitting diodes, increasing the fill factor FF of solar cells, short-circuit current J SC , open-circuit voltage V OC , power conversion efficiency PCE , increasing the detection sensitivity of photodetectors and other parameters.

根据本发明的一方面,提出一种基于极性界面实现钙钛矿薄膜和发光器件优化的方法,以发光薄膜和发光二极管为例,具体说明将极性界面引入衬底或者电荷传输材料和钙钛矿材料之间的方法,及通过测试仪器表征引入极性界面后使得钙钛矿薄膜和钙钛矿器件性能得到调控或优化的方面。According to one aspect of the present invention, a method for optimizing perovskite films and light-emitting devices based on polar interfaces is proposed. Taking light-emitting films and light-emitting diodes as examples, the introduction of polar interfaces into substrates or charge transport materials and calcium The method between the titanite materials, and the performance of the perovskite thin film and the perovskite device can be regulated or optimized after the introduction of the polar interface through the test instrument.

1、极性界面能够调控或优化钙钛矿薄膜的工作原理1. Polar interfaces can tune or optimize the working principle of perovskite thin films

钙钛矿属于极性离子晶体,一般可采用溶液法、热沉积法等方法合成,基于钙钛矿的发光薄膜或光电器件中,钙钛矿是由很多nm或μm尺寸的钙钛矿块体形成致密薄膜,而这些块体又由很多nm尺寸的钙钛矿晶体结晶形成,在钙钛矿由原材料形成结晶块体过程中,外界环境会对结晶有很大影响。钙钛矿在与衬底、电荷传输材料结合时,如果存在晶格不匹配的现象,会带来多方面问题。主要原因表现为两方面,一方面是性能突出的衬底、电荷传输材料和钙钛矿材料不能完美匹配,限制了制备的钙钛矿光电器件的性能,例如对于溶液法制备的光电器件,电荷传输材料、钙钛矿材料存在界面互溶现象,导致界面不完美进而影响到各功能材料的性能;另一方面是钙钛矿材料存在问题,表现为晶体生长质量差、晶界及界面缺陷多,最终限制钙钛矿材料及光电器件的性能。Perovskites are polar ionic crystals and can generally be synthesized by solution methods, thermal deposition methods, etc. In perovskite-based light-emitting films or optoelectronic devices, perovskites are composed of many nm or μm-sized perovskite blocks. Dense films are formed, and these blocks are formed by crystallization of many nm-sized perovskite crystals. In the process of perovskite forming crystalline blocks from raw materials, the external environment will have a great influence on the crystallization. When perovskite is combined with substrate and charge transport material, if there is a phenomenon of lattice mismatch, it will bring many problems. The main reasons are two aspects. On the one hand, the outstanding performance of substrates, charge transport materials and perovskite materials cannot be perfectly matched, which limits the performance of the prepared perovskite optoelectronic devices. For example, for optoelectronic devices prepared by solution methods, the charge Transport materials and perovskite materials have interfacial dissolution phenomenon, which leads to imperfect interface and affects the performance of various functional materials; on the other hand, perovskite materials have problems, which are manifested in poor crystal growth quality, many grain boundaries and interface defects Ultimately limit the performance of perovskite materials and optoelectronic devices.

本发明中采用极性材料作为钙钛矿薄膜及光电器件的界面材料,其主要原因是为了通过极性界面来调控或优化钙钛矿薄膜或光电器件的性能,钙钛矿主要结构式为ABX3,其中A为有机或无机阳离子,B为金属阳离子,X为卤化物阴离子,不同材料A、B、X的结合导致钙钛矿晶体也是极性材料。根据相似相容原理,钙钛矿可以和极性材料很好的配合。自然中不同材料所包含的元素电负性之差会导致形成的材料呈现不同的极性,在化学中,极性是指一根共价键或一个共价分子中由于电荷分布的不均匀性所带来的正负电荷中心不重合现象。如果电荷分布得不均匀,则该键或分子表现为极性;如果电荷分布的很均匀,则表现为非极性。物质的一些物理性质(如溶解性、熔沸点等)与分子的极性相关。对于极性共价分子,说明其内部电荷分布不均匀或者正负电荷中心没有重合,分子的极性取决于分子内各个键的极性以及它们的排列方式,且极性会影响到与其相近的材料的正负电荷中心的移动。In the present invention, the polar material is used as the interface material of the perovskite thin film and the optoelectronic device, and the main reason is to regulate or optimize the performance of the perovskite thin film or optoelectronic device through the polar interface. The main structural formula of the perovskite is ABX 3 , where A is an organic or inorganic cation, B is a metal cation, and X is a halide anion. The combination of different materials A, B, and X leads to perovskite crystals that are also polar materials. According to the similar compatibility principle, perovskites can cooperate well with polar materials. The difference in the electronegativity of elements contained in different materials in nature will lead to the formation of materials with different polarities. In chemistry, polarity refers to a covalent bond or a covalent molecule due to the inhomogeneity of charge distribution. The resulting positive and negative charge centers do not coincide. If the charge distribution is uneven, the bond or molecule appears polar; if the charge distribution is very even, the bond or molecule appears nonpolar. Some physical properties of substances (such as solubility, melting point, etc.) are related to the polarity of the molecule. For polar covalent molecules, it means that the internal charge distribution is not uniform or the positive and negative charge centers do not overlap. The polarity of the molecule depends on the polarity of each bond in the molecule and their arrangement, and the polarity will affect the adjacent ones. The movement of the positive and negative charge centers of a material.

材料的极性不同会影响到材料表面能,表面能是形成物质表面时对分子间化学键破坏的度量。在固体物理理论中,表面原子比物质内部的原子具有更多的能量,因此,根据能量最低原理,原子会自发的趋于物质内部而不是表面。表面能的另一种定义是,材料表面相对于材料内部所多出的能量。把一个固体材料分解成小块需要破坏它内部的化学键,所以需要消耗能量。如果这个分解的过程是可逆的,那么把材料分解成小块所需要的能量同小块材料表面所增加的能量相等,即表面能增加。但事实上,只有在真空中刚刚形成的表面才符合能量守恒定律。因为新形成的表面是非常不稳定的,他们通过表面原子重组和相互间的反应,或者对周围其他分子或原子的吸附,从而使表面能量降低。对于材料中,由于表面层原子朝向外面的键能没有得到补偿,使得表面质点比体内质点具有额外的势能,由于物体表面积改变而引起的内能改变,单位面积的表面能的数值和表面张力相同,但两者物理意义不同,但是可以通过表面张力来间接研究表面能。The difference in polarity of materials affects the surface energy of the material, which is a measure of the breakdown of chemical bonds between molecules when the surface of a substance is formed. In the theory of solid state physics, atoms on the surface have more energy than atoms inside the material, so according to the principle of minimum energy, atoms will spontaneously tend to the inside of the material rather than the surface. Another definition of surface energy is the excess energy on the surface of a material relative to the interior of the material. Breaking a solid material into smaller pieces requires breaking the chemical bonds within it, so it takes energy. If this decomposition process is reversible, then the energy required to decompose the material into small pieces is equal to the energy added to the surface of the small pieces of material, that is, the surface energy increases. But in fact, only surfaces that have just formed in a vacuum obey the law of conservation of energy. Because the newly formed surfaces are very unstable, they reduce the surface energy through the reorganization of surface atoms and their reactions with each other, or the adsorption of other molecules or atoms around them. For materials, since the bond energy of the surface layer atoms toward the outside is not compensated, the surface particles have additional potential energy than the internal particles, and the internal energy changes due to the change of the surface area of the object, the value of the surface energy per unit area is the same as the surface tension , but the two have different physical meanings, but the surface energy can be indirectly studied through surface tension.

由于部分衬底、电荷传输材料表面能较低,在某些电荷传输材料表面存在的非极性有机基团也会造成表面能降低,均不利于钙钛矿材料铺展,导致钙钛矿材料生长的不致密、覆盖率低、面缺陷和体缺陷密度较多,进而导致分子吸附力下降,最终会带来钙钛矿材料很容易脱落、发花以及局部无覆盖的现象。在这些通过在具有低表面能的衬底、电荷传输材料表面引入极性界面,可以起到修饰衬底、电荷传输材料表面的作用,同时可以和钙钛矿材料合适的匹配,可以减小钙钛矿材料在这些衬底、电荷传输材料上的接触角,进而增加钙钛矿材料在这些衬底、电荷传输材料表面的浸润性,使得钙钛矿材料与衬底、电荷传输材料结合的更加牢固,不容易剥落,使得钙钛矿材料生长的更致密、覆盖率增加、面缺陷和体缺陷密度减少。Due to the low surface energy of some substrates and charge transport materials, the non-polar organic groups existing on the surface of some charge transport materials will also reduce the surface energy, which is not conducive to the spreading of perovskite materials, resulting in the growth of perovskite materials. It is not dense, the coverage is low, and the density of surface defects and bulk defects is high, which leads to a decrease in the molecular adsorption force, which will eventually lead to the phenomenon that the perovskite material is easy to fall off, bloom, and partially uncovered. In these, by introducing polar interfaces on the surface of substrates and charge transport materials with low surface energy, it can play a role in modifying the surfaces of substrates and charge transport materials, and at the same time, it can be properly matched with perovskite materials, which can reduce calcium The contact angle of the perovskite material on these substrates and charge transport materials further increases the wettability of the perovskite material on the surfaces of these substrates and charge transport materials, making the perovskite material more closely combined with the substrate and the charge transport material. It is firm and not easy to peel off, which makes the perovskite material grow denser, increase the coverage, and reduce the density of surface defects and bulk defects.

通过不同极性的界面材料,可以调控钙钛矿生长的致密性、表面覆盖率、面缺陷和体缺陷密度,同时在极性界面上的钙钛矿可有效生长到浸润性不好的聚合物电荷传输材料上。采用强极性界面材料可以诱导与钙钛矿材料的生长方向,从而增加钙钛矿晶体材料生长的指向性和致密性,表现为增加钙钛矿薄膜的载流子寿命、增加钙钛矿薄膜的外量子效率PLQE,进而增加钙钛矿薄膜的稳定性和基于钙钛矿的光电器件性能。Through the interface materials of different polarities, the density, surface coverage, surface defect and bulk defect density of perovskite growth can be regulated. At the same time, the perovskite on the polar interface can be effectively grown to polymers with poor wettability. on charge transport materials. The use of a strongly polar interface material can induce the growth direction of the perovskite material, thereby increasing the directionality and density of the perovskite crystal material growth, which is manifested as increasing the carrier lifetime of the perovskite film and increasing the perovskite film. The external quantum efficiency PLQE, which in turn increases the stability of perovskite films and the performance of perovskite-based optoelectronic devices.

极性界面采用热蒸镀、磁控溅射、MOCVD、ALD、喷涂、印刷、化学合成等物理或化学的方法,沉积到钙钛矿或电荷传输材料上,典型沉积厚度范围为0.1 nm ~ 1000nm,对于目前多数功能材料为纳米级别的器件,可满足当前大部分光电器件的功能需求。相比于直接沉积到SiO2衬底上的钙钛矿薄膜缺陷多、晶体取向性差,极性界面起到调控晶体生长的作用,极性界面与极性钙钛矿相匹配可增加薄膜质量,可增加晶体钙钛矿生长尺寸、减少面缺陷和体缺陷密度,且不会影响薄膜本身的光谱特性及组分,使得钙钛矿薄膜可有效抑制非辐射复合、增加辐射复合,进而增加薄膜载流子荧光寿命,实现更高光致外量子效率。极性界面由于隔绝电荷传输材料和钙钛矿材料,可减少衬底或传输材料对钙钛矿薄膜的荧光淬灭。The polar interface is deposited on the perovskite or charge transport material by physical or chemical methods such as thermal evaporation, magnetron sputtering, MOCVD, ALD, spraying, printing, chemical synthesis, and the typical deposition thickness ranges from 0.1 nm to 1000 nm. , for most of the current functional materials are nanoscale devices, which can meet the functional requirements of most of the current optoelectronic devices. Compared with the perovskite film deposited directly on the SiO2 substrate, there are many defects and poor crystal orientation, and the polar interface plays a role in regulating the crystal growth. The matching of the polar interface with the polar perovskite can increase the film quality. It can increase the growth size of crystalline perovskite, reduce the density of surface defects and bulk defects, and will not affect the spectral characteristics and components of the film itself, so that the perovskite film can effectively inhibit non-radiative recombination, increase radiative recombination, and then increase the film loading. The lifetime of the carrier fluorescence is higher, and the higher photo-induced external quantum efficiency is achieved. The polar interface can reduce the fluorescence quenching of the perovskite film by the substrate or the transport material due to the isolation of the charge transport material and the perovskite material.

极性界面可使得钙钛矿材料和电荷传输材料有效匹配,基于极性界面制备的光电器件,其界面会调控电荷传输材料和钙钛矿材料间注入势垒,调控或增加电荷传输能力。极性界面作为非常薄的隧穿材料,无论在PN型材料还是PIN型材料中,均不会限制载流子的流动。如果利用较厚的极性界面材料,可以利用其双极性特性,对空穴或电子部分阻挡以实现器件中电荷平衡,实现传输电荷调控以平衡电子空穴的传输速率,可提高钙钛矿光电子器件的性能,例如降低发光二极管的开启电压V T 、提高太阳能电池的填充因子FF、短路电流J SC 、开路电压V OC 、功率转化效率PCE、增加光电探测器的探测灵敏度等参数。The polar interface can effectively match the perovskite material and the charge transport material. In optoelectronic devices prepared based on the polar interface, the interface can regulate the injection barrier between the charge transport material and the perovskite material, and regulate or increase the charge transport capability. As a very thin tunneling material, the polar interface will not restrict the flow of carriers in either PN-type or PIN-type materials. If a thicker polar interface material is used, its bipolar properties can be used to partially block holes or electrons to achieve charge balance in the device, and to achieve charge transfer regulation to balance the electron-hole transport rate, which can improve perovskite. The performance of optoelectronic devices, such as reducing the turn - on voltage VT of light-emitting diodes, increasing the fill factor FF of solar cells, short-circuit current J SC , open-circuit voltage V OC , power conversion efficiency PCE , increasing the detection sensitivity of photodetectors and other parameters.

2、引入极性界面后亲水性实验的制备方法及表征2. Preparation method and characterization of hydrophilicity experiment after introducing polar interface

图3所示为极性界面的亲水性实验制备流程图。极性界面是沉积到无导电玻璃ITO的石英片上,石英片尺寸为12mm*12mm,石英片在使用前用去离子水、丙酮、异丙醇、去离子水、异丙醇步骤进行15分钟超声清洗。清洗完成的石英片放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗,随之将石英片转移到充满高纯氮的手套箱,并选择要进行蒸镀的极性界面材料,接下来转移到真空镀膜机中进行极性界面蒸镀,直至蒸镀完成。真空蒸镀的气压为5 x 10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.01 nm/s,极性界面LiF蒸镀厚度为1 nm。Figure 3 shows the flow chart of the hydrophilic experimental preparation of the polar interface. The polar interface is deposited on a quartz piece without conductive glass ITO. The size of the quartz piece is 12mm*12mm. The quartz piece is sonicated for 15 minutes with deionized water, acetone, isopropanol, deionized water, and isopropanol before use. cleaning. The cleaned quartz wafer was placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning, and then the quartz wafer was transferred to a glove box filled with high-purity nitrogen, and the polar interface material to be evaporated was selected, and then transferred The polar interface evaporation is carried out in a vacuum coating machine until the evaporation is completed. The pressure of vacuum evaporation was 5 x 10 -4 Pa, the evaporation rate was measured by quartz crystal, the evaporation rate was 0.01 nm/s, and the thickness of LiF evaporation at the polar interface was 1 nm.

图4所示为添加界面前和添加界面后的亲水性浸润实验对比,采用的测试溶液为DMSO,可以看到添加界面后的衬底浸润性得到了加强,表明添加界面后,溶剂更容易铺展开,而钙钛矿是溶解于DMSO溶剂中,故钙钛矿在极性界面上会与衬底结合的更加紧密。Figure 4 shows the comparison of the hydrophilic wetting experiments before and after adding the interface. The test solution used is DMSO. It can be seen that the wettability of the substrate after adding the interface is enhanced, indicating that after adding the interface, the solvent is easier Spread out, and the perovskite is dissolved in the DMSO solvent, so the perovskite will be more closely combined with the substrate at the polar interface.

3、电荷传输材料用极性界面和等离子体分别进行表面处理的对比表征3. Comparative characterization of charge transport materials with polar interface and plasma surface treatments, respectively

图5为采用极性界面和等离子体分别进行表面处理流程图。由于选用的电荷传输材料表面能比较低,电荷传输材料名称为聚(9,9-二辛基芴-alt-N-(4-仲丁基苯基)-二苯胺)(简称为TFB),钙钛矿材料不容易铺展开,导致薄膜覆盖不完全,一般采用等离子体进行表面处理增加表面能,使得钙钛矿涂覆更加完整。电荷传输材料TFB是制备在石英玻璃上,石英玻璃的尺寸为12mm*12mm,石英玻璃在使用前用去离子水、丙酮、异丙醇、去离子水、异丙醇5个步骤进行15分钟超声清洗。清洗完成的石英玻璃放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗,之后将石英玻璃转移到充满高纯氮的手套箱,将石英玻璃放到真空旋涂机上进行电荷传输材料旋涂。电荷传输材料TFB是溶解在氯苯溶液(简称CB)中,浓度为6mg/ml,涂覆电荷传输材料TFB时,用量程100uL的移液枪吸取30uL的电荷传输溶液涂覆到ITO导电玻璃上,开启真空旋涂机以3000 rpm/s转速旋涂60 s,旋涂完成电荷传输材料的ITO导电玻璃放置到热台上进行120 ℃退火10 min,得到厚度为10nm的平整电荷传输材料TFB薄膜。Figure 5 is a flow chart of surface treatment using polar interface and plasma, respectively. Due to the relatively low surface energy of the selected charge transport material, the name of the charge transport material is poly(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine) (abbreviated as TFB). The perovskite material is not easy to spread, resulting in incomplete film coverage. Generally, plasma surface treatment is used to increase the surface energy, making the perovskite coating more complete. The charge transport material TFB is prepared on quartz glass, the size of the quartz glass is 12mm*12mm, and the quartz glass is sonicated for 15 minutes with 5 steps of deionized water, acetone, isopropanol, deionized water, and isopropanol before use. cleaning. The cleaned quartz glass was placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning, then the quartz glass was transferred to a glove box filled with high-purity nitrogen, and the quartz glass was placed on a vacuum spin coater for spin coating of charge transport materials. The charge transport material TFB is dissolved in chlorobenzene solution (CB for short) with a concentration of 6mg/ml. When coating the charge transport material TFB, use a pipette with a range of 100uL to draw 30uL of charge transport solution and coat it on the ITO conductive glass , turn on the vacuum spin coater and spin at 3000 rpm/s for 60 s, and place the ITO conductive glass with the charge transport material after spin coating on a hot stage for annealing at 120 °C for 10 min to obtain a flat charge transport material TFB film with a thickness of 10 nm. .

随后将覆盖有电荷传输材料的石英玻璃转移到真空镀膜机中进行极性界面LiF蒸镀。真空蒸镀的气压为5 x 10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.01 nm/s,极性界面LiF蒸镀厚度为1nm,直至蒸镀完成。The quartz glass covered with charge transport material was then transferred into a vacuum coater for polar interfacial LiF evaporation. The pressure of vacuum evaporation was 5 x 10 -4 Pa, the evaporation rate was measured by a quartz crystal oscillator, the evaporation rate was 0.01 nm/s, and the thickness of LiF evaporation at the polar interface was 1 nm until the evaporation was completed.

作为对比实验的电荷传输材料衬底则直接用等离子体清洗机进行表面处理5s时间。The charge transport material substrate used as a comparative experiment was directly treated with a plasma cleaner for 5 s.

图6所示为采用LiF极性界面和等离子体进行表面处理的电荷传输材料表面形貌SEM图,由于TFB及其衍生物作为传输特性比较突出的空穴传输材料,但是采用DMSO作为溶剂的钙钛矿与TFB不兼容,钙钛矿不能直接沉积到基于TFB及其衍生物的功能材料上,一般做法是采用Plasma等离子体表面清洗机和UV-Ozone表面清洗机进行表面处理,但是表面处理后会破坏表面形貌,形成比较多的孔洞,导致与钙钛矿接触时增加注入势垒或在界面位置形成面缺陷或体缺陷,从而导致器件的性能下降。采用LiF界面处理的TFB空穴传输材料更加致密,降低了器件漏电的可能,且不会改变电荷传输材料的性能。同时以LiF为代表的极性界面作为隧穿层,会降低电荷的注入势垒,从而能够将性能优异的电荷传输材料和钙钛矿材料友好匹配,实现器件整体性能提升。Figure 6 shows the SEM image of the surface morphology of the charge transport material treated with LiF polar interface and plasma. Because TFB and its derivatives are used as hole transport materials with outstanding transport properties, but calcium ion using DMSO as a solvent Titanium is not compatible with TFB, and perovskite cannot be directly deposited on functional materials based on TFB and its derivatives. The general practice is to use Plasma plasma surface cleaner and UV-Ozone surface cleaner for surface treatment, but after surface treatment It will destroy the surface morphology and form more holes, which will increase the injection barrier or form surface defects or bulk defects at the interface when in contact with the perovskite, resulting in the degradation of device performance. The TFB hole transport material treated with LiF interface is more dense, which reduces the possibility of device leakage without changing the performance of the charge transport material. At the same time, the polar interface represented by LiF acts as a tunneling layer, which will reduce the charge injection barrier, so that the charge transport material with excellent performance and perovskite material can be friendly matched, and the overall performance of the device can be improved.

4、钙钛矿在不同极性界面上的SEM测试对比及表征4. SEM test comparison and characterization of perovskite on interfaces of different polarities

图7为旋涂钙钛矿发光薄膜查看SEM流程图。发光薄膜是沉积到无导电玻璃ITO的石英片上,石英片尺寸为12mm*12mm,石英片在使用前用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇步骤进行15分钟超声清洗。清洗完成的石英片放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗,随之将石英片转移到充满高纯氮的手套箱,并选择要进行蒸镀的极性界面材料,接下来转移到真空镀膜机中进行极性界面分别蒸镀实验,极性界面材料分别为LiF、CaF2、NaF、CsF、MgO,作为对比的石英玻璃SiO2则不进行蒸镀实验。真空蒸镀的气压为5 x 10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.01 nm/s,极性界面蒸镀厚度均为1 nm,蒸镀完极性界面的石英片再转移到充满高纯氮的手套箱旋涂钙钛矿材料。Figure 7 shows the SEM flow chart of the spin-coated perovskite luminescent film. The luminescent film is deposited on a quartz sheet without conductive glass ITO, the size of the quartz sheet is 12mm*12mm, and the quartz sheet is treated with deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, isopropanol before use. The propanol step was sonicated for 15 min. The cleaned quartz wafer was placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning, and then the quartz wafer was transferred to a glove box filled with high-purity nitrogen, and the polar interface material to be evaporated was selected, and then transferred In the vacuum coating machine, the polar interface evaporation experiments were carried out, and the polar interface materials were LiF, CaF 2 , NaF, CsF, and MgO. As a comparison, the quartz glass SiO 2 was not subjected to evaporation experiments. The pressure of vacuum evaporation is 5 x 10 -4 Pa, the evaporation rate is measured by a quartz crystal oscillator, the evaporation rate is 0.01 nm/s, and the evaporation thickness of the polar interface is 1 nm. The sheets were then transferred to a glove box filled with high-purity nitrogen to spin-coat the perovskite material.

钙钛矿前驱体溶液为PEAnCsPbnBr3n+1,其由110mg的溴化铅(PbBr2)、64mg的溴化铯(CsBr)和24mg的2-苯乙基溴化铵(PEABr)溶解在1mL的二甲基亚砜(DMSO)溶液中,溶液浓度为0.3 mol/L,溶液放置于60℃热台上搅拌1h。旋涂时将石英片放到真空旋涂机上,将配好的前驱体钙钛矿溶液涂到蒸镀有极性界面的石英片上,以3000 rpm/s转速旋涂60 s,旋涂完成钙钛矿材料的石英玻璃放置到热台上进行60 ℃退火10 min,得到厚度为35 nm的平整钙钛矿材料薄膜。The perovskite precursor solution is PEA n CsPbn Br 3n+1 , which consists of 110 mg of lead bromide (PbBr 2 ), 64 mg of cesium bromide (CsBr) and 24 mg of 2-phenethylammonium bromide (PEABr) Dissolved in 1 mL of dimethyl sulfoxide (DMSO) solution, the concentration of the solution was 0.3 mol/L, and the solution was placed on a hot stage at 60 °C and stirred for 1 h. When spin coating, put the quartz sheet on the vacuum spin coater, apply the prepared precursor perovskite solution to the quartz sheet with polar interface, spin at 3000 rpm/s for 60 s, and complete the spin coating. The quartz glass of titanium ore material was placed on a hot stage for annealing at 60 °C for 10 min, and a flat perovskite material film with a thickness of 35 nm was obtained.

图8所示为钙钛矿在不同界面上的成膜SEM形貌,采用的衬底为石英片SiO2,在强极性界面LiF、CaF2、NaF、CsF上沉积钙钛矿后,均能够形成致密的薄膜,意味着基于极性界面的器件会有很好的界面,降低漏电的概率,在石英片SiO2和弱极性界面MgO上沉积的钙钛矿则存在较多的孔洞,在形成的器件中会引起漏电现象,所以强极性界面可以起到调控钙钛矿生长的作用,起到诱导钙钛矿结晶的过程,进而改变钙钛矿生长的形貌。Figure 8 shows the SEM morphologies of perovskite films formed on different interfaces. The substrate used is quartz sheet SiO 2 . The ability to form dense films means that devices based on polar interfaces will have a good interface and reduce the probability of leakage. Perovskite deposited on quartz sheet SiO 2 and weakly polar interface MgO has more holes, The leakage phenomenon will be caused in the formed device, so the strong polar interface can play a role in regulating the growth of perovskite, inducing the process of perovskite crystallization, and then changing the morphology of perovskite growth.

5、钙钛矿在不同极性界面上的Wavelength测试对比及表征5. Wavelength test comparison and characterization of perovskite on interfaces of different polarities

图9为旋涂钙钛矿发光薄膜测试Wavelength流程图。发光薄膜是沉积到无导电玻璃ITO的石英片上,石英片尺寸为12mm*12mm,石英片在使用前用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇步骤进行15分钟超声清洗。清洗完成的石英片放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗,随之将石英片转移到充满高纯氮的手套箱,并选择要进行蒸镀的极性界面材料,接下来转移到真空镀膜机中进行极性界面分别蒸镀实验,极性界面材料分别为Cs2CO3、LiF、CaF2、NaF、KF、CsF,作为对比的石英玻璃SiO2(命名为None)则不进行蒸镀实验。真空蒸镀的气压为5 x 10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.01 nm/s,极性界面蒸镀厚度均为1 nm,蒸镀完极性界面的石英片再转移到充满高纯氮的手套箱旋涂钙钛矿材料。Figure 9 is a flow chart of the Wavelength test of spin-coated perovskite luminescent thin films. The luminescent film is deposited on a quartz sheet without conductive glass ITO, the size of the quartz sheet is 12mm*12mm, and the quartz sheet is treated with deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, isopropanol before use. The propanol step was sonicated for 15 min. The cleaned quartz wafer was placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning, and then the quartz wafer was transferred to a glove box filled with high-purity nitrogen, and the polar interface material to be evaporated was selected, and then transferred Go to the vacuum coating machine to carry out the evaporation experiments of polar interfaces respectively. The polar interface materials are Cs 2 CO 3 , LiF, CaF 2 , NaF, KF, CsF, respectively. As a comparison, the quartz glass SiO 2 (named as None) is not. Evaporation experiments were carried out. The pressure of vacuum evaporation is 5 x 10 -4 Pa, the evaporation rate is measured by a quartz crystal oscillator, the evaporation rate is 0.01 nm/s, and the evaporation thickness of the polar interface is 1 nm. The sheets were then transferred to a glove box filled with high-purity nitrogen to spin-coat the perovskite material.

钙钛矿前驱体溶液为PEAnCsPbnBr3n+1,其由110mg的溴化铅(PbBr2)、64mg的溴化铯(CsBr)和24mg的2-苯乙基溴化铵(PEABr)溶解在1mL的二甲基亚砜(DMSO)溶液中,溶液浓度为0.3 mol/L,溶液放置于60℃热台上搅拌1h。旋涂时将石英片放到真空旋涂机上,将配好的前驱体钙钛矿溶液涂到蒸镀有极性界面的石英片上,以3000 rpm/s转速旋涂60 s,旋涂完成钙钛矿材料的石英玻璃放置到热台上进行60 ℃退火10 min,得到厚度为35 nm的平整钙钛矿材料薄膜。The perovskite precursor solution is PEA n CsPbn Br 3n+1 , which consists of 110 mg of lead bromide (PbBr 2 ), 64 mg of cesium bromide (CsBr) and 24 mg of 2-phenethylammonium bromide (PEABr) Dissolved in 1 mL of dimethyl sulfoxide (DMSO) solution, the concentration of the solution was 0.3 mol/L, and the solution was placed on a hot stage at 60 °C and stirred for 1 h. When spin coating, put the quartz sheet on the vacuum spin coater, apply the prepared precursor perovskite solution to the quartz sheet with polar interface, spin at 3000 rpm/s for 60 s, and complete the spin coating. The quartz glass of titanium ore material was placed on a hot stage for annealing at 60 °C for 10 min, and a flat perovskite material film with a thickness of 35 nm was obtained.

发光薄膜的光谱测量是通过亮度计实现,将蒸镀完成钙钛矿的石英片放到亮度计测试台,用365 nm紫外光激发荧光薄膜,亮度计光谱检测范围为380 nm ~ 950 nm,可完全覆盖样品发光范围。The spectral measurement of the luminescent film is realized by a luminance meter. The perovskite-deposited quartz sheet is placed on the luminance meter test bench, and the fluorescent film is excited by 365 nm ultraviolet light. Complete coverage of the sample luminescence range.

图10所示为生长在不同极性界面上的材料的PL光谱,光谱测量仪器为亮度计,横轴为波长Wavelength,单位为nm,纵轴为归一化的光谱强度Normalized PL。由图5中钙钛矿的发光光谱基本没有发生变化,说明极性界面不会改变钙钛矿的结晶组分。Figure 10 shows the PL spectra of materials grown on interfaces of different polarities. The spectral measuring instrument is a luminance meter, the horizontal axis is the wavelength Wavelength, in nm, and the vertical axis is the normalized spectral intensity Normalized PL. The luminescence spectrum of the perovskite in Figure 5 is basically unchanged, indicating that the polar interface does not change the crystalline composition of the perovskite.

6、钙钛矿在不同极性界面上的Absorbance吸收测试步骤及表征6. Absorbance test steps and characterization of perovskite on interfaces of different polarities

图11为旋涂钙钛矿发光薄膜测试Absorbance流程图。发光薄膜是沉积到无导电玻璃ITO的石英片上,石英片尺寸为12mm*12mm,石英片在使用前用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇步骤进行15分钟超声清洗。清洗完成的石英片放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗,随之将石英片转移到充满高纯氮的手套箱,并选择要进行蒸镀的极性界面材料,接下来转移到真空镀膜机中进行极性界面分别蒸镀实验,极性界面材料分别为LiF、CaF2、NaF、KF、CsF,作为对比试验的石英玻璃SiO2无极性界面材料。真空蒸镀的气压为5 x 10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.01 nm/s,极性界面蒸镀厚度均为1 nm,蒸镀完极性界面的石英片再转移到充满高纯氮的手套箱旋涂钙钛矿材料。Figure 11 is the flow chart of the Absorbance test of the spin-coated perovskite luminescent film. The luminescent film is deposited on a quartz sheet without conductive glass ITO, the size of the quartz sheet is 12mm*12mm, and the quartz sheet is treated with deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, isopropanol before use. The propanol step was sonicated for 15 min. The cleaned quartz wafer was placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning, and then the quartz wafer was transferred to a glove box filled with high-purity nitrogen, and the polar interface material to be evaporated was selected, and then transferred The polar interface was vapor-deposited in a vacuum coating machine, and the polar interface materials were LiF, CaF 2 , NaF, KF, and CsF, which were used as the quartz glass SiO 2 non-polar interface material for the comparative test. The pressure of vacuum evaporation is 5 x 10 -4 Pa, the evaporation rate is measured by a quartz crystal oscillator, the evaporation rate is 0.01 nm/s, and the evaporation thickness of the polar interface is 1 nm. The sheets were then transferred to a glove box filled with high-purity nitrogen to spin-coat the perovskite material.

钙钛矿前驱体溶液为PEAnCsPbnBr3n+1,其由110mg的溴化铅(PbBr2)、64mg的溴化铯(CsBr)和24mg的2-苯乙基溴化铵(PEABr)溶解在1mL的二甲基亚砜(DMSO)溶液中,溶液浓度为0.3 mol/L,溶液放置于60℃热台上搅拌1h。旋涂时将石英片放到真空旋涂机上,将配好的前驱体钙钛矿溶液涂到蒸镀有极性界面的石英片上,以3000 rpm/s转速旋涂60 s,旋涂完成钙钛矿材料的石英玻璃放置到热台上进行60 ℃退火10 min,得到厚度为35 nm的平整钙钛矿材料薄膜。The perovskite precursor solution is PEA n CsPbn Br 3n+1 , which consists of 110 mg of lead bromide (PbBr 2 ), 64 mg of cesium bromide (CsBr) and 24 mg of 2-phenethylammonium bromide (PEABr) Dissolved in 1 mL of dimethyl sulfoxide (DMSO) solution, the concentration of the solution was 0.3 mol/L, and the solution was placed on a hot stage at 60 °C and stirred for 1 h. When spin coating, put the quartz sheet on the vacuum spin coater, apply the prepared precursor perovskite solution to the quartz sheet with polar interface, spin at 3000 rpm/s for 60 s, and complete the spin coating. The quartz glass of titanium ore material was placed on a hot stage for annealing at 60 °C for 10 min, and a flat perovskite material film with a thickness of 35 nm was obtained.

薄膜的吸收测量是通过紫外可见分光光度计实现,将蒸镀完成钙钛矿的石英片放到分光光度计测试台,激发光谱范围为190nm ~ 1100 nm,可完全覆盖样品发光范围。将覆盖有钙钛矿的石英片放置到紫外分光光度计测试架上,在测试前采用标准石英片进行一步光谱校准以获得更精准的测量,紫外分光光度计可完全覆盖样品吸收光范围。The absorption measurement of the thin film is realized by a UV-visible spectrophotometer. The perovskite-deposited quartz sheet is placed on the test bench of the spectrophotometer. The excitation spectrum ranges from 190 nm to 1100 nm, which can completely cover the emission range of the sample. Place the quartz plate covered with perovskite on the UV spectrophotometer test stand, and use the standard quartz plate to perform one-step spectral calibration before testing to obtain a more accurate measurement. The UV spectrophotometer can completely cover the light absorption range of the sample.

图12所示为生长在不同极性界面上的钙钛矿材料的吸收光谱,自上至下极性界面材料分别为LiF、CaF2、NaF、KF、CsF和SiO2,其中LiF、CaF2、NaF、KF、CsF表示钙钛矿沉积到覆盖有相应极性界面材料的衬底上,SiO2表示钙钛矿沉积到无极性界面材料覆盖的石英基底上。其中吸收光谱测量仪器为紫外分光光度计,横轴为紫外分光光度计发出的光谱Wavelength,单位为nm,纵轴为紫外分光光度计检测到的材料对应当前波长的吸收系数Absorbance。由图6知钙钛矿材料吸收光谱几乎没有变化,说明添加的极性界面并不会改变到发光薄膜的本质结构和组分。Figure 12 shows the absorption spectra of perovskite materials grown on interfaces of different polarities. From top to bottom, the polar interface materials are LiF, CaF 2 , NaF, KF, CsF and SiO 2 , among which LiF, CaF 2 , NaF , KF, CsF denote perovskite deposition onto substrates covered with corresponding polar interface materials, and SiO denotes perovskite deposition onto quartz substrates covered with non-polar interface materials. The absorption spectrum measuring instrument is an ultraviolet spectrophotometer, the horizontal axis is the wavelength of the spectrum emitted by the ultraviolet spectrophotometer, the unit is nm, and the vertical axis is the absorption coefficient Absorbance of the material detected by the ultraviolet spectrophotometer corresponding to the current wavelength. It can be seen from Figure 6 that the absorption spectrum of the perovskite material has almost no change, indicating that the added polar interface does not change the essential structure and composition of the light-emitting film.

7、钙钛矿在不同极性界面上的X光衍射制备步骤及表征(XRD)7. X-ray diffraction preparation and characterization (XRD) of perovskite on interfaces of different polarities

图13为旋涂钙钛矿发光薄膜测试XRD流程图。发光薄膜是沉积到无导电玻璃ITO的石英片上,石英片尺寸为12mm*12mm,石英片在使用前用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇步骤进行15分钟超声清洗。清洗完成的石英片放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗,随之将石英片转移到充满高纯氮的手套箱,并选择要进行蒸镀的极性界面材料,接下来转移到真空镀膜机中进行极性界面分别蒸镀实验,极性界面材料分别为MoO3、ZnO、MgO、Li2CO3、Na2CO3、Cs2CO3、LiF、CaF2、NaF、KF、CsF。真空蒸镀的气压为5 x10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.01 nm/s,极性界面蒸镀厚度均为1 nm,蒸镀完极性界面的石英片再转移到充满高纯氮的手套箱旋涂钙钛矿材料。FIG. 13 is the XRD flow chart of the spin-coated perovskite luminescent thin film test. The luminescent film is deposited on a quartz sheet without conductive glass ITO, the size of the quartz sheet is 12mm*12mm, and the quartz sheet is treated with deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, isopropanol before use. The propanol step was sonicated for 15 min. The cleaned quartz wafer was placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning, and then the quartz wafer was transferred to a glove box filled with high-purity nitrogen, and the polar interface material to be evaporated was selected, and then transferred Go to the vacuum coating machine to carry out the evaporation experiment of polar interface respectively. The polar interface materials are MoO 3 , ZnO, MgO, Li 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , LiF, CaF 2 , NaF, KF , CsF. The pressure of vacuum evaporation was 5 x 10 -4 Pa, the evaporation rate was measured by a quartz crystal oscillator, the evaporation rate was 0.01 nm/s, the thickness of the polar interface evaporation was 1 nm, and the quartz plate with the polar interface was evaporated. Then transfer to a glove box filled with high-purity nitrogen to spin-coat the perovskite material.

钙钛矿前驱体溶液为PEAnCsPbnBr3n+1,其由110mg的溴化铅(PbBr2)、64mg的溴化铯(CsBr)和24mg的2-苯乙基溴化铵(PEABr)溶解在1mL的二甲基亚砜(DMSO)溶液中,溶液浓度为0.3 mol/L,溶液放置于60℃热台上搅拌1h。旋涂时将石英片放到真空旋涂机上,将配好的前驱体钙钛矿溶液涂到蒸镀有极性界面的石英片上,以3000 rpm/s转速旋涂60 s,旋涂完成钙钛矿材料的石英玻璃放置到热台上进行60 ℃退火10 min,得到厚度为35 nm的平整钙钛矿材料薄膜。The perovskite precursor solution is PEA n CsPbn Br 3n+1 , which consists of 110 mg of lead bromide (PbBr 2 ), 64 mg of cesium bromide (CsBr) and 24 mg of 2-phenethylammonium bromide (PEABr) Dissolved in 1 mL of dimethyl sulfoxide (DMSO) solution, the concentration of the solution was 0.3 mol/L, and the solution was placed on a hot stage at 60 °C and stirred for 1 h. When spin coating, put the quartz sheet on the vacuum spin coater, apply the prepared precursor perovskite solution to the quartz sheet with polar interface, spin at 3000 rpm/s for 60 s, and complete the spin coating. The quartz glass of titanium ore material was placed on a hot stage for annealing at 60 °C for 10 min, and a flat perovskite material film with a thickness of 35 nm was obtained.

XRD衍射测量采用的是Bruker设备,测量度数范围为10°-45°,测量步进间隔为0.02°,测量时间为5°/min,测量电压为40kV,测量电流为30mA。The XRD diffraction measurement adopts Bruker equipment, the measurement degree range is 10°-45°, the measurement step interval is 0.02°, the measurement time is 5°/min, the measurement voltage is 40kV, and the measurement current is 30mA.

图14所示为钙钛矿在不同界面上的薄膜XRD,横轴为度数,纵轴为相对强度。自上至下极性界面材料分别为LiF、CaF2、NaF、KF、CsF、SiO2和bkgd,其中LiF、CaF2、NaF、KF、CsF表示钙钛矿沉积到覆盖有相应极性界面材料的衬底上,SiO2表示钙钛矿沉积到无极性界面材料覆盖的石英基底上,bkgd表示无钙钛矿覆盖的石英基底的衍射峰。相比于直接沉积到石英片SiO2衬底上的钙钛矿薄膜,其100和200峰均有增强趋势,但是并没有增加其它峰型的出现,表明极性界面增强了钙钛矿在这些峰的组分,起到了调控钙钛矿薄膜内组分的作用。Figure 14 shows the thin film XRD of perovskite on different interfaces, the horizontal axis is degrees, and the vertical axis is relative intensity. The polar interface materials from top to bottom are LiF, CaF 2 , NaF, KF, CsF, SiO 2 and bkgd, respectively, where LiF, CaF 2 , NaF, KF, CsF represent the perovskite deposited on the surface covered with the corresponding polar interface materials On the substrate of , SiO2 represents the perovskite deposited on the quartz substrate covered with non-polar interface material, and bkgd represents the diffraction peak of the quartz substrate without perovskite covering. Compared with the perovskite film deposited directly on the quartz sheet SiO2 substrate, both the 100 and 200 peaks tend to be enhanced, but the appearance of other peak types is not increased, indicating that the polar interface enhances the perovskite in these The composition of the peak plays a role in regulating the composition in the perovskite film.

8、钙钛矿在不同极性界面上的光致外量子效率PLQE及表征8. Photoinduced external quantum efficiency PLQE and characterization of perovskite at different polar interfaces

图15为不同界面的光致量子效率PLQE测试流程图。发光薄膜是沉积到无导电玻璃ITO的石英片上,石英片尺寸为12mm*12mm,石英片在使用前用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇步骤进行15分钟超声清洗。清洗完成的石英片放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗,随之将石英片转移到充满高纯氮的手套箱,并选择要进行蒸镀的极性界面材料,接下来转移到真空镀膜机中进行极性界面分别蒸镀实验,极性界面材料分别为MoO3、ZnO、MgO、Li2CO3、Na2CO3、Cs2CO3、LiF、CaF2、NaF、KF、CsF。真空蒸镀的气压为5 x 10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.01 nm/s,极性界面蒸镀厚度均为1 nm,蒸镀完极性界面的石英片再转移到充满高纯氮的手套箱旋涂钙钛矿材料。Figure 15 is a flow chart of the photo-induced quantum efficiency PLQE test at different interfaces. The luminescent film is deposited on a quartz sheet without conductive glass ITO, the size of the quartz sheet is 12mm*12mm, and the quartz sheet is treated with deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, isopropanol before use. The propanol step was sonicated for 15 min. The cleaned quartz wafer was placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning, and then the quartz wafer was transferred to a glove box filled with high-purity nitrogen, and the polar interface material to be evaporated was selected, and then transferred Go to the vacuum coating machine to carry out the evaporation experiment of polar interface respectively. The polar interface materials are MoO 3 , ZnO, MgO, Li 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , LiF, CaF 2 , NaF, KF , CsF. The pressure of vacuum evaporation is 5 x 10 -4 Pa, the evaporation rate is measured by a quartz crystal oscillator, the evaporation rate is 0.01 nm/s, and the evaporation thickness of the polar interface is 1 nm. The sheets were then transferred to a glove box filled with high-purity nitrogen to spin-coat the perovskite material.

钙钛矿前驱体溶液为PEAnCsPbnBr3n+1,其由110mg的溴化铅(PbBr2)、64mg的溴化铯(CsBr)和24mg的2-苯乙基溴化铵(PEABr)溶解在1mL的二甲基亚砜(DMSO)溶液中,溶液浓度为0.3 mol/L,溶液放置于60℃热台上搅拌1h。旋涂时将石英片放到真空旋涂机上,将配好的前驱体钙钛矿溶液涂到蒸镀有极性界面的石英片上,以3000 rpm/s转速旋涂60 s,旋涂完成钙钛矿材料的石英玻璃放置到热台上进行60 ℃退火10 min,得到厚度为35 nm的平整钙钛矿材料薄膜。The perovskite precursor solution is PEA n CsPbn Br 3n+1 , which consists of 110 mg of lead bromide (PbBr 2 ), 64 mg of cesium bromide (CsBr) and 24 mg of 2-phenethylammonium bromide (PEABr) Dissolved in 1 mL of dimethyl sulfoxide (DMSO) solution, the concentration of the solution was 0.3 mol/L, and the solution was placed on a hot stage at 60 °C and stirred for 1 h. When spin coating, put the quartz sheet on the vacuum spin coater, apply the prepared precursor perovskite solution to the quartz sheet with polar interface, spin at 3000 rpm/s for 60 s, and complete the spin coating. The quartz glass of titanium ore material was placed on a hot stage for annealing at 60 °C for 10 min, and a flat perovskite material film with a thickness of 35 nm was obtained.

将旋涂完钙钛矿的石英片拿出手套箱测量光致量子效率PLQE,放置到外部积分球进行PLQE测量,积分球系统由Ocean HDX系列光谱仪、405 nm波长连续激光器、10 cm直径积分球、电脑上位机系统组成,采用三步法测量钙钛矿样品的PLQE。Take the perovskite-coated quartz sheet out of the glove box to measure the photo-induced quantum efficiency PLQE, and place it on an external integrating sphere for PLQE measurement. The integrating sphere system is composed of Ocean HDX series spectrometer, 405 nm wavelength continuous laser, and 10 cm diameter integrating sphere. 2. It is composed of a computer host computer system, and a three-step method is used to measure the PLQE of perovskite samples.

图16中所示为钙钛矿的光致外量子效率PLQE随不同极性界面电负性的变化,横轴为极性界面的电负性Difference in electronegativity,纵轴为钙钛矿在极性界面上的光致外量子效率PLQE。其中SiO2界面是钙钛矿直接沉积到石英衬底上。其中在极性界面NiO、MoO3、ZnO、MgO、Li2CO3、Na2CO3上界面会降低钙钛矿的PLQE,说明存在荧光淬灭或者光吸收的过程,影响了钙钛矿的PLQE,随着极性增加,极性界面对钙钛矿的影响越来越小,说明在钙钛矿系统中利用极性界面时需要进行极性匹配。其中在极性界面Cs2CO3、LiF、CaF2、NaF、KF、CsF上均会增加钙钛矿的荧光,相比于SiO2材料界面说明极性界面抑制了非辐射复合,增加了辐射复合,表明强极性界面能够使得钙钛矿薄膜实现更高出光效率,同时随金属活性变化,呈现依次降低的现象,说明在不同金属化合物表面,钙钛矿生长时性能有所下降。在引入几种界面后,对于几种能增强PLQE的界面,其荧光寿命也会增加,说明界面作用使得钙钛矿生长的质量更好,抑制了非辐射复合过程,增强了辐射复合过程,实现了更高的PLQE。Figure 16 shows the photoinduced external quantum efficiency PLQE of perovskite as a function of the electronegativity of different polar interfaces, the horizontal axis is the difference in electronegativity of the polar interface, and the vertical axis is the polar interface Photoinduced external quantum efficiency PLQE at the interface. where the SiO2 interface is perovskite deposited directly onto the quartz substrate. Among them, on the polar interface NiO, MoO 3 , ZnO, MgO, Li 2 CO 3 , Na 2 CO 3 will reduce the PLQE of perovskite, indicating that there is a process of fluorescence quenching or light absorption, which affects the perovskite. PLQE, the polar interface has less and less influence on perovskite as the polarity increases, indicating that polarity matching is required when utilizing polar interfaces in perovskite systems. Among them, the fluorescence of perovskite will increase on the polar interface Cs 2 CO 3 , LiF, CaF 2 , NaF, KF and CsF. Compared with the SiO 2 material interface, the polar interface inhibits the non-radiative recombination and increases the radiation. The composite shows that the strong polar interface can enable the perovskite film to achieve higher light extraction efficiency, and at the same time, with the change of metal activity, it shows a phenomenon of decreasing in turn, indicating that the performance of perovskite decreases when growing on the surface of different metal compounds. After the introduction of several interfaces, the fluorescence lifetime of several interfaces that can enhance PLQE will also increase, indicating that the interface effect makes the perovskite growth quality better, suppresses the non-radiative recombination process, and enhances the radiative recombination process. higher PLQE.

9、钙钛矿在不同界面上的荧光寿命测试制备方法及测试表征9. Preparation method and test characterization of fluorescence lifetime test of perovskite on different interfaces

图17为钙钛矿在不同电荷传输材料上的制备步骤。发光薄膜在不同界面上的荧光寿命测试是基于石英衬底、电荷传输层PVK、电荷传输层TFB/LiF这3种结构,石英片尺寸为12mm*12mm,石英片在使用前用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇步骤进行15分钟超声清洗。清洗完成的石英片放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗。Figure 17 shows the preparation steps of perovskite on different charge transport materials. The fluorescence lifetime test of the luminescent film on different interfaces is based on three structures: quartz substrate, charge transport layer PVK, and charge transport layer TFB/LiF. The size of the quartz sheet is 12mm*12mm. The steps of acetone, isopropanol, deionized water, isopropanol, deionized water, and isopropanol were ultrasonically cleaned for 15 minutes. The cleaned quartz wafers were placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning.

钙钛矿前驱体溶液为PEAnCsPbnBr3n+1,其由110mg的溴化铅(PbBr2)、64mg的溴化铯(CsBr)和24mg的2-苯乙基溴化铵(PEABr)溶解在1mL的二甲基亚砜(DMSO)溶液中,溶液浓度为0.3 mol/L,溶液放置于60℃热台上搅拌1h。The perovskite precursor solution is PEA n CsPbn Br 3n+1 , which consists of 110 mg of lead bromide (PbBr 2 ), 64 mg of cesium bromide (CsBr) and 24 mg of 2-phenethylammonium bromide (PEABr) Dissolved in 1 mL of dimethyl sulfoxide (DMSO) solution, the concentration of the solution was 0.3 mol/L, and the solution was placed on a hot stage at 60 °C and stirred for 1 h.

①对于无电荷传输层和界面的钙钛矿样品,则直接旋涂钙钛矿溶液。① For perovskite samples without charge transport layer and interface, the perovskite solution is directly spin-coated.

②对于添加电荷传输层PVK的样品,需要先旋涂电荷传输材料PVK,电荷传输材料PVK是溶解在氯苯溶液(简称CB)中,浓度为6mg/ml,涂覆电荷传输材料PVK时,用量程100uL的移液枪吸取30uL的电荷传输溶液涂覆到石英玻璃上,开启真空旋涂机以3000 rpm/s转速旋涂60 s,旋涂完成电荷传输材料的石英玻璃放置到热台上进行120 ℃退火10 min,得到厚度为10 nm的平整电荷传输材料PVK薄膜。之后用量程100uL的移液枪吸取30uL的钙钛矿溶液涂覆到石英玻璃上,开启真空旋涂机以3000 rpm/s转速旋涂60 s,旋涂完成钙钛矿材料的石英玻璃放置到热台上进行60 ℃退火10 min,得到厚度为35 nm的平整钙钛矿材料薄膜。②For samples with added charge transport layer PVK, it is necessary to spin-coat the charge transport material PVK first. The charge transport material PVK is dissolved in chlorobenzene solution (CB for short) at a concentration of 6mg/ml. When coating the charge transport material PVK, use A pipette with a range of 100uL draws 30uL of charge transport solution and coats it on the quartz glass. Turn on the vacuum spin coater and spin at 3000 rpm/s for 60 s. After the spin coating is completed, the quartz glass of the charge transport material is placed on a hot stage. After annealing at 120 ℃ for 10 min, a flat PVK film with a thickness of 10 nm was obtained. Then use a pipette with a range of 100uL to draw 30uL of perovskite solution and coat it on the quartz glass, turn on the vacuum spin coater and spin at 3000 rpm/s for 60 s, and place the quartz glass of the perovskite material after the spin coating is completed. Annealed at 60 °C for 10 min on a hot stage to obtain a flat perovskite material film with a thickness of 35 nm.

③对于添加电荷传输层TFB/LiF的样品,需要先旋涂电荷传输材料TFB,电荷传输材料TFB是溶解在氯苯溶液(简称CB)中,浓度为6mg/ml,涂覆电荷传输材料TFB时,用量程100uL的移液枪吸取30uL的电荷传输溶液涂覆到石英玻璃上,开启真空旋涂机以3000 rpm/s转速旋涂60 s,旋涂完成电荷传输材料的石英玻璃放置到热台上进行120 ℃退火10 min,得到厚度为10 nm的平整电荷传输材料TFB薄膜。③ For the samples with the charge transport layer TFB/LiF added, the charge transport material TFB needs to be spin-coated first. The charge transport material TFB is dissolved in a chlorobenzene solution (CB for short) at a concentration of 6 mg/ml. When coating the charge transport material TFB , use a pipette with a range of 100uL to draw 30uL of charge transfer solution and coat it on the quartz glass, turn on the vacuum spin coater and spin at 3000 rpm/s for 60 s, and place the quartz glass of the charge transfer material after spin coating on the hot stage. Annealed at 120 °C for 10 min to obtain a flat charge transport material TFB film with a thickness of 10 nm.

随之将石英片转移到充满高纯氮的手套箱,接下来转移到真空镀膜机中进行极性界面LiF蒸镀。真空蒸镀的气压为5 x 10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.01 nm/s,极性界面蒸镀厚度为1 nm,蒸镀完极性界面的石英片再转移到充满高纯氮的手套箱旋涂钙钛矿材料。Subsequently, the quartz sheets were transferred to a glove box filled with high-purity nitrogen, and then transferred to a vacuum coater for polar interfacial LiF evaporation. The pressure of vacuum evaporation was 5 x 10 -4 Pa, the evaporation rate was measured by a quartz crystal oscillator, the evaporation rate was 0.01 nm/s, the thickness of the polar interface evaporation was 1 nm, and the quartz plate with the polar interface was evaporated. Then transfer to a glove box filled with high-purity nitrogen to spin-coat the perovskite material.

用量程100uL的移液枪吸取30uL的钙钛矿溶液涂覆到石英玻璃上,开启真空旋涂机以3000 rpm/s转速旋涂60 s,旋涂完成钙钛矿材料的石英玻璃放置到热台上进行60 ℃退火10 min,得到厚度为35 nm的平整钙钛矿材料薄膜。Use a pipette with a range of 100uL to draw 30uL of perovskite solution onto the quartz glass, turn on the vacuum spin coater and spin at 3000 rpm/s for 60 s. After annealing at 60 °C for 10 min on the stage, a flat perovskite material film with a thickness of 35 nm was obtained.

发光薄膜的荧光寿命测量是通过时间相关单光子计数器TCSPC实现,将制备的薄膜样品石英片放置到荧光寿命测量样品测试架,用405 nm脉冲激光激发样品,脉冲激光频率范围为20 kHz ~ 2 MHz,脉冲激光在2MHz时平均功率为6mW,样品薄膜发光测量采用单光子计数器探头测量,探头为雪崩光电二极管APD,供电采用+12 V,未采用雪崩光电二极管的倍增因子是为了减少探测器暗电流引入的背底噪声信号,对于APD输出的光-电信号采用差分放大电路进行信号放大,以脉冲整形电路、脉冲滤波电路进行脉冲整形、脉冲滤波再进行一级T型放大,提取出具有高信噪比的荧光-电信号,通过同轴电缆线将电信号输入TCSPC主机进行发光薄膜样品的荧光寿命读取。The fluorescence lifetime measurement of the luminescent film is realized by the time-correlated single photon counter TCSPC. The prepared film sample quartz plate is placed in the fluorescence lifetime measurement sample test stand, and the sample is excited with a 405 nm pulsed laser with a frequency range of 20 kHz to 2 MHz. , the average power of the pulsed laser at 2MHz is 6mW, the luminescence measurement of the sample thin film is measured by a single photon counter probe, the probe is an avalanche photodiode APD, the power supply is +12 V, and the multiplication factor of the avalanche photodiode is not used to reduce the dark current of the detector For the introduced background noise signal, the optical-electrical signal output by the APD is amplified by the differential amplifier circuit, and the pulse shaping circuit and the pulse filter circuit are used for pulse shaping and pulse filtering, and then a T-type amplification is performed to extract the signal with high signal. The fluorescence-to-electrical signal of the noise ratio, the electric signal is input into the TCSPC host through the coaxial cable to read the fluorescence lifetime of the luminescent film sample.

图18所示为钙钛矿在不同界面上的荧光寿命,单位为ns,纵轴为对应电压下的电流密度Current density,单位为mA cm-2。对比了PVK/perovskite、TFB/LiF/perovskite、perovskite的荧光寿命,其中PVK、TFB为电荷传输材料,LiF为极性界面,perovskite为钙钛矿,在石英衬底和PVK衬底上的钙钛矿具有接近的荧光寿命,而在TFB/LiF上的钙钛矿具有最长的荧光寿命,表明LiF作为极性界面会诱导钙钛矿的结晶,调控了钙钛矿的生长过程,进而减少了缺陷态密度,从而增加了荧光寿命。Figure 18 shows the fluorescence lifetime of perovskite at different interfaces, the unit is ns, and the vertical axis is the current density at the corresponding voltage, the unit is mA cm -2 . The fluorescence lifetimes of PVK/perovskite, TFB/LiF/perovskite, and perovskite were compared, in which PVK and TFB were charge transport materials, LiF was polar interface, and perovskite was perovskite. Perovskite on quartz substrate and PVK substrate Ore has a close fluorescence lifetime, while perovskite on TFB/LiF has the longest fluorescence lifetime, indicating that LiF acts as a polar interface to induce perovskite crystallization, regulating the growth process of perovskite, which in turn reduces the density of defect states, thereby increasing the fluorescence lifetime.

10、不同厚度极性界面器件的制备方法及测试表征10. Preparation method and test characterization of polar interface devices with different thicknesses

图19为不同厚度界面的制备流程图。发光二极管是制备在ITO导电玻璃上,ITO导电玻璃的尺寸为12mm*12mm,ITO导电玻璃在使用前用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇7个步骤进行15分钟超声清洗。清洗完成的ITO导电玻璃放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗,之后将ITO导电玻璃转移到充满高纯氮的手套箱,将ITO导电玻璃放到真空旋涂机上进行电荷传输材料旋涂,电荷传输材料名称为聚(9,9-二辛基芴-alt-N-(4-仲丁基苯基)-二苯胺)(简称为TFB)。TFB是溶解在氯苯溶液(简称CB)中,浓度为6mg/ml,涂覆电荷传输材料TFB时,用量程100uL的移液枪吸取30uL的电荷传输溶液涂覆到ITO导电玻璃上,开启真空旋涂机以3000 rpm/s转速旋涂60 s,旋涂完成电荷传输材料的ITO导电玻璃放置到热台上进行120 ℃退火10 min,得到平整的电荷传输材料TFB薄膜。Figure 19 is a flow chart of the fabrication of interfaces with different thicknesses. The light-emitting diode is prepared on the ITO conductive glass, the size of the ITO conductive glass is 12mm*12mm, the ITO conductive glass is used with deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, isopropanol before use. 7 steps of propanol for 15 min ultrasonic cleaning. The cleaned ITO conductive glass was placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning, then the ITO conductive glass was transferred to a glove box filled with high-purity nitrogen, and the ITO conductive glass was placed on a vacuum spin coater for charge transfer material. Spin coating, the charge transport material name is poly(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine) (abbreviated as TFB). TFB is dissolved in chlorobenzene solution (CB for short) with a concentration of 6mg/ml. When coating the charge transport material TFB, use a pipette with a range of 100uL to draw 30uL of charge transport solution onto the ITO conductive glass, and turn on the vacuum. The spin coating machine was used for spin coating at 3000 rpm/s for 60 s, and the ITO conductive glass with charge transport material after spin coating was placed on a hot stage for annealing at 120 °C for 10 min to obtain a flat TFB film of charge transport material.

随后将覆盖有电荷传输材料的ITO导电玻璃转移到真空镀膜机中进行极性界面LiF蒸镀。真空蒸镀的气压为5 x 10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.01nm/s,极性界面LiF蒸镀厚度为0nm、1nm、2nm、5nm。蒸镀完极性界面LiF的ITO导电玻璃衬底再转移到充满高纯氮的手套箱进行钙钛矿溶液旋涂。The ITO conductive glass covered with charge transport material was then transferred into a vacuum coater for polar interfacial LiF evaporation. The pressure of vacuum evaporation is 5 x 10 -4 Pa, the evaporation rate is measured by a quartz crystal oscillator, the evaporation rate is 0.01nm/s, and the thickness of the polar interface LiF evaporation is 0nm, 1nm, 2nm, 5nm. After evaporation of polar interface LiF, the ITO conductive glass substrate was transferred to a glove box filled with high-purity nitrogen for spin coating of perovskite solution.

将旋涂完钙钛矿的ITO导电玻璃再放入真空镀膜机进行电荷传输材料蒸镀,电荷传输材料名称为2,2',2“-(1,3,5-苯并咪唑)-三(1-苯基-1-H-苯并咪唑)(简称为TPBi),真空蒸镀的气压为5 x 10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.1 nm/s,TPBi的厚度为40nm。Put the spin-coated perovskite ITO conductive glass into a vacuum coating machine for charge transport material evaporation. The charge transport material is named 2,2', 2"-(1,3,5-benzimidazole)-three (1-Phenyl-1-H-benzimidazole) (abbreviated as TPBi), the pressure of vacuum evaporation is 5 x 10 -4 Pa, the evaporation rate is measured by a quartz crystal, and the evaporation rate is 0.1 nm/s , the thickness of TPBi is 40 nm.

蒸镀完电荷传输材料TPBi后,更换蒸镀的金属掩膜版,通过掩膜版可限制发光尺寸为5.25mm2,蒸镀电极材料氟化锂LiF和Al,蒸镀速率由石英晶振片测量,氟化锂LiF蒸镀速率为0.01 nm/s,LiF的厚度为1nm,金属铝Al蒸镀的厚度为100nm。After evaporating the charge transport material TPBi, replace the deposited metal mask. The mask can limit the luminous size to 5.25mm 2 . The electrode materials are lithium fluoride, LiF and Al, and the evaporation rate is measured by a quartz crystal oscillator. , the lithium fluoride LiF evaporation rate is 0.01 nm/s, the thickness of LiF is 1 nm, and the thickness of metal aluminum Al evaporation is 100 nm.

制备完成的器件在测试时采用OLED光色电测试系统测试外量子效率EQE,发光二极管的效率测试是由OLED 2000光色电外量子效率测试系统实现,系统包括亮度计、吉时利源表2400、电脑上位机、工控摄像头CCD、样品测试台等组成,亮度计用以检测发光二极管的光谱及光谱功率,吉时利源表2400作为发光二极管动力源,承担动力输出和电流检测的功能,以2400引出正负极接线后连接发光二极管正负极,加载到发光器件上的电压范围为0 V~8 V,电压步进间隔为0.1 V,通过发光二极管的电流以四线法测量,电流检测范围1nA ~100 mA,电流密度范围为10-3 – 103 mA/cm2,故可满足发光二极管电流测试需求。电脑上位机实现与亮度计、吉时利源表2400、工控摄像头CCD交互通讯的功能,获取采集的光谱、光谱功率、电压、电流及检测图像,并实现实时显示功能,样品测试台承担发光二极管样品放置,达到三维位置调节功能,使得观察更清晰、测量更准确,以实现最优化性能测试目的。The prepared device is tested by the OLED photochromic test system to test the external quantum efficiency EQE. The efficiency test of the light-emitting diode is realized by the OLED 2000 photochromic external quantum efficiency test system, which includes a luminance meter, a Keithley source meter 2400 , computer host computer, industrial control camera CCD, sample test bench, etc. The luminance meter is used to detect the spectrum and spectral power of light-emitting diodes. The 2400 leads the positive and negative terminals and then connects the positive and negative terminals of the light-emitting diode. The voltage applied to the light-emitting device ranges from 0 V to 8 V, and the voltage step interval is 0.1 V. The current through the light-emitting diode is measured by the four-wire method, and the current is detected. The range is 1nA ~ 100 mA, and the current density range is 10 -3 – 10 3 mA/cm 2 , so it can meet the current testing requirements of light-emitting diodes. The computer host computer realizes the function of interactive communication with the luminance meter, Keithley source meter 2400, and industrial control camera CCD, obtains the collected spectrum, spectral power, voltage, current and detection images, and realizes the real-time display function. The sample test bench is responsible for light-emitting diodes The sample is placed to achieve the three-dimensional position adjustment function, which makes the observation clearer and the measurement more accurate, so as to achieve the purpose of optimizing the performance test.

图20所示为不同厚度的界面对电荷注入能力的影响,横轴为加载到发光二极管两端的电压Voltage,单位为V,纵轴为对应电压下的电流密度Current density,单位为mAcm-2。在添加了LiF极性界面后,采用LiF的厚度为0nm、1nm、2nm、5nm,其电荷传输能力得到大幅度提升,在2V后电流密度迅速增加,表现为随电压变化的电流密度斜率增大,表明其电荷注入能力得到加强,对比电流密度曲线随电压的变化,比无LiF材料的斜率更高,说明超薄的LiF材料能够增加电荷有效注入,另外改变界面厚度后,其电荷传输能力并没有变化,说明极性界面是作为隧穿层的存在,并不会影响到电荷注入及增加势垒。Figure 20 shows the effect of interfaces with different thicknesses on the charge injection capability. The horizontal axis is the voltage applied to both ends of the LED, in V, and the vertical axis is the current density at the corresponding voltage, in mAcm -2 . After adding LiF polar interface, the thickness of LiF is 0nm, 1nm, 2nm, 5nm, and its charge transport ability is greatly improved, and the current density increases rapidly after 2V, which shows that the slope of current density increases with voltage. , indicating that its charge injection ability has been enhanced, and the slope of the contrast current density curve with voltage is higher than that of the material without LiF, indicating that the ultra-thin LiF material can increase the effective charge injection. In addition, after changing the interface thickness, its charge transport ability and There is no change, indicating that the polar interface exists as a tunneling layer, and will not affect the charge injection and increase the potential barrier.

11、极性界面用于发光器件的制备方法及测试表征11. Preparation method and test characterization of polar interface for light-emitting devices

图21为发光二极管器件制备流程图。发光二极管是制备在ITO导电玻璃上,ITO导电玻璃的尺寸为12mm*12mm,ITO导电玻璃在使用前用去离子水、丙酮、异丙醇、去离子水、异丙醇、去离子水、异丙醇7个步骤进行15分钟超声清洗。清洗完成的ITO导电玻璃放到UV-Ozone臭氧清洗机中进行15分钟臭氧清洗,之后将ITO导电玻璃转移到充满高纯氮的手套箱,将ITO导电玻璃放到真空旋涂机上进行电荷传输材料旋涂,电荷传输材料名称为聚(9,9-二辛基芴-alt-N-(4-仲丁基苯基)-二苯胺)(简称为TFB)。TFB是溶解在氯苯溶液(简称CB)中,浓度为6mg/ml,涂覆电荷传输材料TFB时,用量程100uL的移液枪吸取30uL的电荷传输溶液涂覆到ITO导电玻璃上,开启真空旋涂机以3000 rpm/s转速旋涂60 s,旋涂完成电荷传输材料的ITO导电玻璃放置到热台上进行120 ℃退火10 min,得到平整的电荷传输材料TFB薄膜。FIG. 21 is a flow chart of the fabrication of the light emitting diode device. The light-emitting diode is prepared on the ITO conductive glass, the size of the ITO conductive glass is 12mm*12mm, the ITO conductive glass is used with deionized water, acetone, isopropanol, deionized water, isopropanol, deionized water, isopropanol before use. 7 steps of propanol for 15 min ultrasonic cleaning. The cleaned ITO conductive glass was placed in a UV-Ozone ozone cleaning machine for 15 minutes of ozone cleaning, then the ITO conductive glass was transferred to a glove box filled with high-purity nitrogen, and the ITO conductive glass was placed on a vacuum spin coater for charge transfer material. Spin coating, the charge transport material name is poly(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine) (abbreviated as TFB). TFB is dissolved in chlorobenzene solution (CB for short) with a concentration of 6mg/ml. When coating the charge transport material TFB, use a pipette with a range of 100uL to draw 30uL of charge transport solution onto the ITO conductive glass, and turn on the vacuum. The spin coating machine was used for spin coating at 3000 rpm/s for 60 s, and the ITO conductive glass with charge transport material after spin coating was placed on a hot stage for annealing at 120 °C for 10 min to obtain a flat TFB film of charge transport material.

随后将覆盖有电荷传输材料的ITO导电玻璃转移到真空镀膜机中进行极性界面LiF蒸镀。真空蒸镀的气压为5 x 10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.01nm/s,极性界面LiF蒸镀厚度为1nm。蒸镀完极性界面LiF的ITO导电玻璃衬底再转移到充满高纯氮的手套箱进行钙钛矿溶液旋涂。The ITO conductive glass covered with charge transport material was then transferred into a vacuum coater for polar interfacial LiF evaporation. The pressure of vacuum evaporation was 5 x 10 -4 Pa, the evaporation rate was measured by a quartz crystal oscillator, the evaporation rate was 0.01 nm/s, and the thickness of LiF evaporation at the polar interface was 1 nm. After evaporation of polar interface LiF, the ITO conductive glass substrate was transferred to a glove box filled with high-purity nitrogen for spin coating of perovskite solution.

钙钛矿前驱体溶液为PEAnCsPbnBr3n+1,其由110mg的溴化铅(PbBr2)、64mg的溴化铯(CsBr)和24mg的2-苯乙基溴化铵(PEABr)溶解在1mL的二甲基亚砜(DMSO)溶液中,溶液浓度为0.3 mol/L,溶液放置于60℃热台上搅拌1h。旋涂时将ITO导电玻璃放到真空旋涂机上,用量程100uL吸取30uL溶液涂覆到蒸镀有极性界面和电荷传输材料的ITO导电玻璃上,开启真空旋涂机按钮以3000 rpm/s转速旋涂60 s,60 ℃退火10 min即可得到平整的钙钛矿薄膜。The perovskite precursor solution is PEA n CsPbn Br 3n+1 , which consists of 110 mg of lead bromide (PbBr 2 ), 64 mg of cesium bromide (CsBr) and 24 mg of 2-phenethylammonium bromide (PEABr) Dissolved in 1 mL of dimethyl sulfoxide (DMSO) solution, the concentration of the solution was 0.3 mol/L, and the solution was placed on a hot stage at 60 °C and stirred for 1 h. When spin coating, put the ITO conductive glass on the vacuum spin coater, draw 30uL of solution with a measuring range of 100uL and coat it on the ITO conductive glass evaporated with polar interface and charge transport material, turn on the vacuum spin coater button at 3000 rpm/s Spin-coating for 60 s at a rotational speed and annealing at 60 °C for 10 min can obtain a flat perovskite film.

将旋涂完钙钛矿的ITO导电玻璃再放入真空镀膜机进行电荷传输材料蒸镀,电荷传输材料名称为2,2',2“-(1,3,5-苯并咪唑)-三(1-苯基-1-H-苯并咪唑)(简称为TPBi),真空蒸镀的气压为5 x 10-4 Pa,蒸镀速率由石英晶振片测量,蒸镀速率为0.1 nm/s,TPBi的厚度为40nm。Put the spin-coated perovskite ITO conductive glass into a vacuum coating machine for charge transport material evaporation. The charge transport material is named 2,2', 2"-(1,3,5-benzimidazole)-three (1-Phenyl-1-H-benzimidazole) (abbreviated as TPBi), the pressure of vacuum evaporation is 5 x 10 -4 Pa, the evaporation rate is measured by a quartz crystal, and the evaporation rate is 0.1 nm/s , the thickness of TPBi is 40 nm.

蒸镀完电荷传输材料TPBi后,更换蒸镀的金属掩膜版,通过掩膜版可限制发光尺寸为5.25mm2,蒸镀电极材料氟化锂LiF和Al,蒸镀速率由石英晶振片测量,氟化锂LiF蒸镀速率为0.01 nm/s,LiF的厚度为1nm,金属铝Al蒸镀的厚度为100nm。After evaporating the charge transport material TPBi, replace the deposited metal mask. The mask can limit the luminous size to 5.25mm 2 . The electrode materials are lithium fluoride, LiF and Al, and the evaporation rate is measured by a quartz crystal oscillator. , the lithium fluoride LiF evaporation rate is 0.01 nm/s, the thickness of LiF is 1 nm, and the thickness of metal aluminum Al evaporation is 100 nm.

制备完成的器件在测试时采用OLED光色电测试系统测试外量子效率EQE,发光二极管的效率测试是由OLED 2000光色电外量子效率测试系统实现,系统包括亮度计、吉时利源表2400、电脑上位机、工控摄像头CCD、样品测试台等组成,亮度计用以检测发光二极管的光谱及光谱功率,吉时利源表2400作为发光二极管动力源,承担动力输出和电流检测的功能,以2400引出正负极接线后连接发光二极管正负极,加载到发光器件上的电压范围为0 V~8 V,电压步进间隔为0.1 V,通过发光二极管的电流以四线法测量,电流检测范围1nA ~100 mA,电流密度范围为10-3 – 103 mA/cm2,故可满足发光二极管电流测试需求。电脑上位机实现与亮度计、吉时利源表2400、工控摄像头CCD交互通讯的功能,获取采集的光谱、光谱功率、电压、电流及检测图像,并实现实时显示功能,样品测试台承担发光二极管样品放置,达到三维位置调节功能,使得观察更清晰、测量更准确,以实现最优化性能测试目的。The prepared device is tested by the OLED photochromic test system to test the external quantum efficiency EQE. The efficiency test of the light-emitting diode is realized by the OLED 2000 photochromic external quantum efficiency test system, which includes a luminance meter, a Keithley source meter 2400 , computer host computer, industrial control camera CCD, sample test bench, etc. The luminance meter is used to detect the spectrum and spectral power of light-emitting diodes. The 2400 leads the positive and negative terminals and then connects the positive and negative terminals of the light-emitting diode. The voltage applied to the light-emitting device ranges from 0 V to 8 V, and the voltage step interval is 0.1 V. The current through the light-emitting diode is measured by the four-wire method, and the current is detected. The range is 1nA ~ 100 mA, and the current density range is 10 -3 – 10 3 mA/cm 2 , so it can meet the current testing requirements of light-emitting diodes. The computer host computer realizes the function of interactive communication with the luminance meter, Keithley source meter 2400, and industrial control camera CCD, obtains the collected spectrum, spectral power, voltage, current and detection images, and realizes the real-time display function. The sample test bench is responsible for light-emitting diodes The sample is placed to achieve the three-dimensional position adjustment function, which makes the observation clearer and the measurement more accurate, so as to achieve the purpose of optimizing the performance test.

图22所示为基于极性界面传输材料和其它传输材料的器件效率,横轴为通过发光二极管的电流密度Current density,单位为mA cm-2,纵轴为外量子效率EQE,单位为%。发光二极管结构为ITO/HTL/Perovskite/TPBi/LiF/Al,其中HTL为空穴传输材料,分别为TFB/LiF、PVK两种结构,从曲线看出,由于TFB的空穴迁移率比PVK为高,较高空穴迁移率会增加低电压下电荷的传输能力。采用极性界面LiF沉积到TFB上具有最高的效率,说明以LiF替换PVK使得电荷更好的注入到钙钛矿功能材料中,减少了传输材料界面和钙钛矿材料的势垒。Figure 22 shows the device efficiencies based on polar interface transport materials and other transport materials. The horizontal axis is the current density through the light-emitting diode, in mA cm -2 , and the vertical axis is the external quantum efficiency, EQE, in %. The structure of the light-emitting diode is ITO/HTL/Perovskite/TPBi/LiF/Al, in which HTL is a hole transport material, which are TFB/LiF and PVK respectively. It can be seen from the curve that the hole mobility of TFB is higher than that of PVK. High, higher hole mobility increases the charge transport capability at low voltages. Deposition of LiF on TFB with polar interface has the highest efficiency, indicating that replacing PVK with LiF enables better charge injection into the perovskite functional material and reduces the barrier of the transport material interface and the perovskite material.

Claims (8)

1. A halide perovskite optoelectronic device based on a polar interface, characterized in that: the preparation process of the perovskite luminescent thin film luminescent device comprises the following steps:
preparation of the substrate: firstly, respectively carrying out ultrasonic cleaning for 15 minutes by using seven steps of deionized water, acetone, isopropanol, deionized water and isopropanol, then putting the substrate into a UV-Ozone cleaning machine for carrying out Ozone cleaning for 15 minutes, then transferring the substrate into a vacuum coating machine for carrying out polar interface evaporation, wherein the evaporation process in the vacuum coating machine is finished in a glove box, and obtaining the substrate with the polar interface after evaporation;
and transferring the substrate with the evaporated polar interface to a glove box filled with high-purity nitrogen to spin-coat the perovskite thin film: when the perovskite is coated in a spin mode, the substrate coated with the polar interface in a vapor deposition mode is placed on a vacuum spin coating machine, the perovskite precursor solution absorbed by a liquid transfer gun is dripped onto the substrate coated with the polar interface in a vapor deposition mode, the vacuum spin coating machine carries out spin coating for 60s at the rotating speed of 3000 rpm/s, then the substrate coated with the perovskite in a spin mode is placed on a hot bench to be annealed for 10min at the temperature of 60 ℃, and the perovskite luminescent thin film luminescent device is obtained.
2. The polar interface based halide perovskite optoelectronic device of claim 1, wherein: the polar interface material is composed of a plurality of compounds, including polar interface materials capable of forming compounds during different periods, polar interface materials capable of forming compounds among different groups, strong polar interface materials capable of forming compounds among different groups, and other interface materials matched with perovskite materials.
3. A polar interface based halide perovskite optoelectronic device as claimed in claim 2 wherein: polar interface materials that can form compounds during different cycles include metal oxide material interface ZrO2、V2O5、Al2O3、NiO、MoO3、ZnO、MgO、NiO、SnO2(ii) a The polar interface material capable of forming compound between different groups comprises carbonate metal compound material Li2CO3、Na2CO3、 Cs2CO3(ii) a The strong polar interface materials which can form compounds among different groups comprise metal fluoride material interfaces LiF, NaF, KF, RbF, CsF and MgF2、CaF2(ii) a Other interface materials that interact with perovskite materials include PTFE, piezoelectric films, piezoelectric ceramics.
4. The polar interface based halide perovskite optoelectronic device of claim 1, wherein: preparing a conductive perovskite luminescent thin film luminescent device with ITO:
a. conductive substrate with ITO: sputtering an ITO raw material onto a substrate by using a magnetron sputtering technology, placing the substrate on a substrate table with a mask plate, partially shielding the substrate by using the mask plate, and partially sputtering an ITO material to be exposed;
b. cleaning treatment of a conductive substrate: carrying out pretreatment on a conductive substrate, firstly carrying out ultrasonic cleaning for 15 minutes by using seven steps of deionized water, acetone, isopropanol, deionized water and isopropanol, and then putting the conductive substrate into a UV-Ozone cleaning machine for carrying out Ozone cleaning for 15 minutes;
c. preparing a charge transport material film: placing the cleaned conductive substrate into a glass culture dish, conveying the glass culture dish into a nitrogen glove box through a transition bin of the glove box, then placing the conductive substrate on a vacuum spin-coating machine in the nitrogen glove box, dissolving a charge transfer material in a solvent, sucking a charge transfer material solution by using a liquid-moving gun, uniformly coating the charge transfer material solution on the conductive substrate, completely coating ITO (indium tin oxide) by using the charge transfer material, starting a button of the vacuum spin-coating machine to spin-coat at 3000rpm for 60s to form a film of the charge transfer material, after the spin-coating of the film of the charge transfer material is completed, placing the conductive substrate covered with the charge transfer material on a heating table to perform high-temperature annealing at 120 ℃ for 10min, and finally forming the ITO-coated charge transfer material film on the conductive substrate;
d. evaporating polar interface materials: opening a bin gate of the vacuum coating machine in the glove box in the first step, placing the conductive substrate which is taken down from the hot table and is prepared with the charge transmission material into a glass culture dish, conveying the conductive substrate into the glove box with the vacuum coating machine through a transition bin, taking out the conductive substrate prepared with the charge transmission material, placing the conductive substrate on an evaporation substrate table in the vacuum coating machine, adjusting the position of the evaporation substrate table, and closing a baffle below the substrate table;
e. spin coating a halide perovskite thin film: during spin coating, placing a conductive substrate coated with a polar interface material and a charge transport material by evaporation on a vacuum spin coating machine, uniformly coating a halide perovskite precursor solution absorbed by a liquid transfer gun on the conductive substrate coated with the polar interface material and the charge transport material by evaporation, starting a button of the vacuum spin coating machine, spin-coating for 60s at the rotating speed of 5000rpm to form a halide perovskite thin film, and placing the conductive substrate coated with the halide perovskite, the polar interface material by evaporation and the charge transport material on a hot table for high-temperature annealing at 90 ℃ for 10 min;
f. evaporation of cathode charge transport material: placing the annealed conductive substrate covered with halide perovskite, evaporated with polar interface material and covered with charge transfer material into a glass culture dish, transferring the substrate into a glove box with a vacuum coating machine through a transition bin, taking the substrate out of the glass culture dish, placing the substrate on an evaporation substrate table in the vacuum coating machine, adjusting the position of the evaporation substrate table, and closing a baffle below the substrate table; the evaporation rate of the charge transport material detected by the quartz crystal oscillator plate is displayed by the film thickness instrument, after the evaporation rate of the charge transport material displayed by the film thickness instrument is stable, the evaporation rate is stable at 0.05nm/s, a baffle below a base plate table in a vacuum coating machine is started, and the charge transport material with uniform evaporation rate can be uniformly deposited on a conductive substrate covered with halide perovskite, evaporated with a polar interface material and covered with the charge transport material;
g. evaporating an electrode: after the charge transmission material is evaporated, the charge transmission material is placed on a metal mask plate in a vacuum coating machine, the evaporation rate of an electrode detected by a quartz crystal oscillation plate is displayed through a film thickness meter, after the evaporation rate of the electrode displayed by the film thickness meter is stable, the evaporation rate is stable at 0.2nm/s, a baffle below a base plate table in the vacuum coating machine is opened, and the electrode with uniform evaporation rate is uniformly deposited on a conductive substrate covered with the charge transmission material, halide perovskite, an evaporated polar interface material and the charge transmission material.
5. A polar interface based halide perovskite optoelectronic device as claimed in claim 1 or 4 wherein: the preparation method of the polar interface on the substrate adopts magnetron sputtering, MOCVD, ALD, spraying, printing or chemical synthesis methods, and the thickness range is 0.1 nm-1000 nm.
6. A polar interface based halide perovskite optoelectronic device as claimed in claim 1 or 4 wherein: the polarity of the polar interface material is changed by regulating and controlling materials with different electronegativities, or a non-polar interface is regulated and controlled to be a polar interface, and finally the final performance of the device is regulated and controlled by changing the polarity mode of the material interface.
7. A polar interface based halide perovskite optoelectronic device as claimed in claim 1 or 4 wherein: the polar material interface is applied to various photoelectric devices, including solar cells, light emitting diodes, detectors, fluorescent films, fluorescent powder, semiconductor transistors, lasers and other photoelectric devices and materials.
8. A polar interface based halide perovskite optoelectronic device as claimed in claim 1 or 4 wherein: the polar material interface can be applied to defining the effective working area of perovskite materials or devices, further defining different working patterns, and can be expanded to be applied to perovskite materials and photoelectric devices based on different patterns.
CN202010503089.9A 2020-06-05 2020-06-05 Halide perovskite optoelectronic devices based on polar interfaces Pending CN111740019A (en)

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