CN107591481B - Preparation method of organometallic halide perovskite thin films doped with barium titanate - Google Patents
Preparation method of organometallic halide perovskite thin films doped with barium titanate Download PDFInfo
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- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 32
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010409 thin film Substances 0.000 title claims abstract description 11
- -1 organometallic halide Chemical class 0.000 title claims description 6
- 239000010408 film Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000004528 spin coating Methods 0.000 claims abstract description 9
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 7
- 150000005309 metal halides Chemical class 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 5
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 230000010287 polarization Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004408 titanium dioxide Substances 0.000 abstract description 3
- 230000005693 optoelectronics Effects 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- 239000011575 calcium Substances 0.000 abstract 1
- 230000005684 electric field Effects 0.000 abstract 1
- 229910052861 titanite Inorganic materials 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 230000005621 ferroelectricity Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
本发明公开了一种掺杂钛酸钡的有机金属卤化物钙钛矿薄膜材料制备方法，属于半导体光电材料和杂化钙钛矿太阳能电池制备领域。采用掺杂的方法把钛酸钡材料加入到钙钛矿材料当中，使其均匀的分散到钙钛矿溶液当中，然后采用旋涂的方法在介孔二氧化钛薄膜上旋涂含有钛酸钡的钙钛矿层，作为太阳能电池的光吸收层材料，本发明通过掺杂改善钙钛矿铁电极性的方法，把具有铁电性的钛酸钡材料加入到钙钛矿层当中，来改善钙钛矿太阳能电池发生光电效应时内部的电场极化状况，提高钙钛矿太阳能电池的稳定性和光电转换效率。
The invention discloses a preparation method of an organic metal halide perovskite thin film material doped with barium titanate, and belongs to the field of preparation of semiconductor optoelectronic materials and hybrid perovskite solar cells. The barium titanate material is added to the perovskite material by doping method to make it uniformly dispersed in the perovskite solution, and then spin-coating method is used to spin-coat the calcium containing barium titanate on the mesoporous titanium dioxide film The titanite layer, as the light absorbing layer material of the solar cell, the present invention improves the perovskite solar energy by adding the ferroelectric barium titanate material into the perovskite layer by doping the method of improving the electrical conductivity of the perovskite iron. The internal electric field polarization state when the photoelectric effect occurs in the battery improves the stability and photoelectric conversion efficiency of the perovskite solar cell.
Description
技术领域technical field
本发明涉及太阳能电池光电转换半导体材料研究的技术领域，特别是杂化钙钛矿太阳能电池的制备方法，属于半导体光电材料和杂化钙钛矿太阳能电池制备领域，尤其涉及一种掺杂钛酸钡的有机金属卤化物钙钛矿薄膜材料制备方法。The invention relates to the technical field of solar cell photoelectric conversion semiconductor material research, in particular to a preparation method of a hybrid perovskite solar cell, belonging to the field of semiconductor optoelectronic materials and the preparation of a hybrid perovskite solar cell, and in particular to a doped titanic acid Barium organometallic halide perovskite thin film material preparation method.
背景技术Background technique
随着传统化石能源的逐步消耗殆尽，以及日益严重地环境污染问题，高效、低能耗、无污染的薄膜太阳能电池受到各国的重视，自从1991年染料敏化太阳能电池(DSSCS)被Michael Gratzel发明且效率突破7％以来，DSSCS以其低成本，相对简单的制备工艺，较高的光电转换效率而备受人们关注，科学家将有机/无机杂化钙钛矿结构引入到太阳能电池中，在短短7年的时间里，效率提高至22.1％；特别是基于CH3NH3I·PbX2(X为Cl、Br或I)等有机/无机杂化钙钛矿薄膜太阳能电池的效率节节攀升，成为当前世界研究的热点。With the gradual exhaustion of traditional fossil energy and the increasingly serious environmental pollution problem, thin-film solar cells with high efficiency, low energy consumption, and no pollution have been paid attention to by various countries. Since its invention and its efficiency exceeded 7%, DSSC S has attracted much attention due to its low cost, relatively simple preparation process and high photoelectric conversion efficiency. Scientists have introduced organic/inorganic hybrid perovskite structure into solar cells, In just 7 years, the efficiency increased to 22.1%; especially the efficiency junction of organic/inorganic hybrid perovskite thin film solar cells based on CH3NH3I · PbX2 (X is Cl , Br or I) It has become a hot spot in current world research.
现有的钙钛矿材料一般有三种晶体结构，包括立方相，四方相，正交相，当前研究普遍认为由于其内部的离子运动，产生铁电极性，影响光伏性能，因此可以通过加入具有铁电性质的材料减少或者改善其铁电极化效应。Existing perovskite materials generally have three crystal structures, including cubic phase, tetragonal phase, and orthorhombic phase. Current research generally believes that due to the movement of ions inside, it produces ferroelectric polarity and affects photovoltaic performance. Therefore, it can be achieved by adding iron. Materials with electrical properties reduce or improve their ferroelectric polarization effects.
钛酸钡(BaTiO3,BTO)是一种典型的钙钛矿型铁电体,其居里点为120℃，熔点为1625℃，其晶体具有良好的铁电性、高介电常数和大的电光系数。因此,BTO薄膜和纳米晶在微电子学和电光集成器件等领域有着十分重要的应用价值。它在室温下为铁电相的四方晶系(4mm点群)，四方相BTO晶体中Ti原子的3d轨道和O的2p轨道之间的相互作用，产生BTO晶体的铁电性。因此，将BTO掺入到有机金属卤化物钙钛矿材料中，成为改善钙钛矿材料铁电极性的首选材料。Barium titanate (BaTiO 3 , BTO) is a typical perovskite ferroelectric with a Curie point of 120 °C and a melting point of 1625 °C. Its crystal has good ferroelectricity, high dielectric constant and large the electro-optic coefficient. Therefore, BTO thin films and nanocrystals have very important application value in the fields of microelectronics and electro-optical integrated devices. It is a tetragonal system (4mm point group) of the ferroelectric phase at room temperature, and the interaction between the 3d orbital of Ti atoms and the 2p orbital of O in the tetragonal BTO crystal produces the ferroelectricity of the BTO crystal. Therefore, the incorporation of BTO into organometallic halide perovskite materials has become the material of choice for improving the ferroelectricity of perovskite materials.
发明内容SUMMARY OF THE INVENTION
本发明目的是提供一种掺杂钛酸钡的有机金属卤化物钙钛矿薄膜的制备方法，针对减弱上述钙钛矿太阳能电池中铁电极性，通过在钙钛矿层中掺入具有铁电性的钛酸钡纳米颗粒，来改善钙钛矿太阳能电池中的铁电极化，提高钙钛矿太阳能电池的光电转换性能。The purpose of the present invention is to provide a preparation method of an organometallic halide perovskite film doped with barium titanate, in order to weaken the iron electrode in the above-mentioned perovskite solar cell, by doping the perovskite layer with a ferroelectricity Barium titanate nanoparticles to improve iron polarization in perovskite solar cells and improve the photoelectric conversion performance of perovskite solar cells.
本发明的设计构思是这样实现的，首先采用掺杂的方法把钛酸钡材料加入到钙钛矿材料当中，使其均匀的分散到钙钛矿溶液当中，然后采用旋涂的方法在介孔二氧化钛薄膜上旋涂含有钛酸钡的钙钛矿层，作为太阳能电池的光吸收层材料，接着旋涂空穴传输层，蒸上银电极，透明导电基底、半导体电子传输层、BTO钙钛矿光吸收层、空穴传输层和银电极，组成掺杂钛酸钡的钙钛矿太阳能电池。The design concept of the present invention is realized in this way. First, the barium titanate material is added to the perovskite material by doping, so that it is uniformly dispersed in the perovskite solution, and then the spin coating method is used in the mesoporous material. A perovskite layer containing barium titanate is spin-coated on the TiO2 film as a light absorbing layer material for solar cells, followed by spin-coating a hole transport layer, and then a silver electrode, transparent conductive substrate, semiconductor electron transport layer, BTO perovskite light The absorber layer, hole transport layer and silver electrode form a perovskite solar cell doped with barium titanate.
为解决上述技术问题，本发明所采用的技术方案是提供一种掺杂钛酸钡的有机金属卤化物钙钛矿薄膜的制备方法，步骤如下：In order to solve the above-mentioned technical problems, the technical solution adopted in the present invention is to provide a preparation method of an organometallic halide perovskite film doped with barium titanate, and the steps are as follows:
取金属卤化物MX2、HC(NH2)2X(简写为FAX)和CH3NH3X(简写为MAX)分别加入到有机溶剂当中，在温度为50～150℃，搅拌0.1～24小时，配制浓度均为0.01～5mol/l的FAMX3和MAMX3溶液，把FAMX3和MAMX3溶液按照浓度比为1:10～10:1的比例混合，在温度为50～150℃，接着搅拌0.1～24小时，得到浓度为0.01～5mol/l的(FAMX3)x(MAMX3)(1-x)混合溶液，把钛酸钡BTO溶液加入到上述混合溶液当中，搅拌0.1～24小时，BTO浓度为0.01～5mol/l，将BTO/(FAMX3)x(MAMX3)(1-x)混合溶液滴加在基底薄膜上，旋转涂膜，转速为500～7500r/min，旋涂时间1～150秒，旋涂后的样品在20～150℃下，热处理5分钟～60分钟。Take the metal halide MX 2 , HC(NH 2 ) 2 X (abbreviated as FAX) and CH 3 NH 3 X (abbreviated as MAX) and add them to the organic solvent respectively, and stir for 0.1 to 24 hours at a temperature of 50 to 150 ° C. , prepare FAMX 3 and MAMX 3 solutions with a concentration of 0.01 to 5 mol/l, mix FAMX 3 and MAMX 3 solutions according to a concentration ratio of 1:10 to 10:1, at a temperature of 50 to 150 ° C, and then stir 0.1 to 24 hours to obtain a (FAMX 3 ) x (MAMX 3 ) (1-x) mixed solution with a concentration of 0.01 to 5 mol/l, adding the barium titanate BTO solution to the above mixed solution, stirring for 0.1 to 24 hours, The concentration of BTO is 0.01～5mol/l, the mixed solution of BTO/(FAMX 3 ) x (MAMX 3 ) (1-x) is dropped on the base film, and the film is spin-coated at a rotational speed of 500～7500r/min, and the spin-coating time is For 1 to 150 seconds, the spin-coated samples are heat-treated at 20 to 150° C. for 5 to 60 minutes.
进一步的，所述方法中的金属卤化物MX2，中M也可以是Sn、Ge、Cu、Cs等一种或几种。Further, in the metal halide MX 2 in the method, M can also be one or more of Sn, Ge, Cu, Cs, etc.
进一步的，所述方法中的MX2、HC(NH2)2X和CH3NH3X中的X可以是I、Br、Cl，也可以是其中一种或者几种的混合物。Further, X in MX 2 , HC(NH 2 ) 2 X and CH 3 NH 3 X in the method can be I, Br, Cl, or one or a mixture of them.
进一步的，所述方法中有机溶剂可以是N-N二甲基甲酰胺溶液，也可以是二甲基亚砜，、γ-丁内酯，也可以是其中两种或者两种以上的混合物。Further, in the method, the organic solvent can be N-N dimethylformamide solution, dimethyl sulfoxide, γ-butyrolactone, or a mixture of two or more of them.
进一步的，所述方法中钛酸钡可以加在FAMX3溶液、也可以加在MAMX3溶液，也可以加在二者混合后的溶液里，也可以加在有机溶剂当中。Further, in the method, barium titanate can be added to the FAMX 3 solution, also can be added to the MAMX 3 solution, can also be added to the mixed solution of the two, or can be added to an organic solvent.
进一步的，所述方法中(FAMX3)x(MAMX3)(1-x)混合溶液中，x数值为1≥x≥0。Further, in the method of (FAMX 3 ) x (MAMX 3 ) (1-x) mixed solution, the value of x is 1≧x≧0.
现有钙钛矿太阳能电池一般通过I-V测量电池的电光电转化效率，但反向扫描时可以获得比正向扫描时更大的填充因子，从而得到较高的光电转化效率，这通常是由电池内部钙钛矿层的铁电极化引起的，这种迟滞效应一般由电池内部结构所造成的，难以消除。本发明通过在钙钛矿层中掺入具有铁电性的钛酸钡纳米颗粒，来改善钙钛矿太阳能电池中的铁电极化，提高钙钛矿太阳能电池的光电转换性能。本发明实验方法工艺简单，操作方便，成本低，制备温度低、薄膜形貌可控，适用于改善钙钛矿太阳能电池铁电极性，提高钙钛矿太阳能电池的稳定性和光电转化效率。Existing perovskite solar cells generally measure the electrical-to-photoelectric conversion efficiency of the cell by I-V, but a larger fill factor can be obtained when scanning in the reverse direction than when scanning in the forward direction, resulting in a higher photoelectric conversion efficiency, which is usually determined by the cell. This hysteresis effect is generally caused by the internal structure of the battery and is difficult to eliminate. The invention improves the iron electrode polarization in the perovskite solar cell and improves the photoelectric conversion performance of the perovskite solar cell by incorporating ferroelectricity barium titanate nanoparticles into the perovskite layer. The experimental method of the invention has the advantages of simple process, convenient operation, low cost, low preparation temperature and controllable film morphology, and is suitable for improving the ferroelectricity of the perovskite solar cell and improving the stability and photoelectric conversion efficiency of the perovskite solar cell.
附图说明Description of drawings
图1是掺杂钛酸钡的钙钛矿(FAMX3)x(MAMX3)(1-x)太阳能电池器件结构图，其中：1-透明导电基底层；2-致密半导体/电子传输层；3-多级孔半导体/电子传输层；4-掺杂钛酸钡的钙钛矿吸光层；5-空穴传输层；6-金属电极层；7-钙钛矿(FAMX3)x(MAMX3)(1-x)吸光层；8-钛酸钡。1 is a structural diagram of a perovskite (FAMX 3 ) x (MAMX 3 ) (1-x) solar cell device doped with barium titanate, wherein: 1-transparent conductive base layer; 2-dense semiconductor/electron transport layer; 3- Hierarchical porous semiconductor/electron transport layer; 4- Perovskite light-absorbing layer doped with barium titanate; 5- Hole transport layer; 6- Metal electrode layer; 7- Perovskite (FAMX 3 ) x (MAMX 3 ) (1-x) Light-absorbing layer; 8-Barium titanate.
图2是实施例1中掺杂钛酸钡的钙钛矿薄膜的扫描电镜(SEM)照片。2 is a scanning electron microscope (SEM) photograph of the perovskite thin film doped with barium titanate in Example 1. FIG.
图3是实施例2中没有掺杂钛酸钡的钙钛矿薄膜的扫描电镜(SEM)照片。FIG. 3 is a scanning electron microscope (SEM) photograph of the perovskite thin film not doped with barium titanate in Example 2. FIG.
图4是实施例1中掺杂钛酸钡的钙钛矿薄膜的X射线衍射(XRD)分析图谱。4 is an X-ray diffraction (XRD) analysis pattern of the perovskite thin film doped with barium titanate in Example 1. FIG.
图5是在AM1.5，100mW/cm2一个太阳标准光照条件下，实施例1中掺杂钛酸钡的钙钛矿太阳能电池的伏安特性J-V曲线。Figure 5 is the JV curve of the volt-ampere characteristics of the perovskite solar cell doped with barium titanate in Example 1 under the standard illumination condition of AM1.5, 100mW/cm 2 of the sun.
表1是实施例1中掺杂钛酸钡的钙钛矿太阳能电池参数。Table 1 shows the parameters of the perovskite solar cell doped with barium titanate in Example 1.
具体实施方式Detailed ways
以下为具体实施例，以便进一步阐述本发明。应理解为，这些实施例仅用于说明本发明而不用于限制本发明的范围，对本发明进行任何改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。The following are specific examples to further illustrate the present invention. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. Any changes or modifications to the present invention, these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
(1)钙钛矿层制备过程(1) Preparation process of perovskite layer
取PbI2、HC(NH2)2I放入烧杯中，加入无水级N-N二甲基甲酰胺和二甲基亚砜，温度为70℃，搅拌12小时，配制浓度为1.3mol/l的FAPbI3液体，取PbI2、CH3NH3I放入烧杯中，加入无水级N-N二甲基甲酰胺和二甲基亚砜，温度为70℃，搅拌12小时，配制浓度为1.3mol/l的MAPbI3液体，将上述溶液按体积比5:1混合，温度为70℃，搅拌12小时，配制(FAPbI3)0.83(MAPbI)0.17溶液，把钛酸钡加入到上述溶液当中，钛酸钡的浓度为0.23mg/mL，将上述溶液滴加在处理好的介孔二氧化钛上，旋转涂膜，转速为1500r/min，旋涂时间30秒，将旋涂后的样品在150℃下，热处理30分钟。通过图2的SEM照片，可以看出BTO已经掺入到钙钛矿薄膜中；图4的XRD数据证明了BTO已经出现在实施例1的复合薄膜中；图5的J-V测试数据显示掺杂BTO的钙钛矿太阳能电池效率为10.72％。Take PbI 2 and HC(NH 2 ) 2 I into a beaker, add anhydrous grade NN dimethylformamide and dimethyl sulfoxide, and stir for 12 hours at a temperature of 70°C to prepare 1.3 mol/l FAPbI 3 liquid, take PbI 2 and CH 3 NH 3 I into a beaker, add anhydrous grade NN dimethylformamide and dimethyl sulfoxide, and stir for 12 hours at a temperature of 70°C to prepare a concentration of 1.3mol/ 1 of MAPbI 3 liquid, mix the above solution by volume ratio 5:1, the temperature is 70 ℃, stir for 12 hours, prepare (FAPbI 3 ) 0.83 (MAPbI) 0.17 solution, add barium titanate into the above solution, titanate The concentration of barium was 0.23 mg/mL, the above solution was added dropwise to the treated mesoporous titanium dioxide, and the film was spin-coated at a rotational speed of 1500 r/min, and the spin-coating time was 30 seconds. Heat treatment for 30 minutes. Through the SEM photo of Fig. 2, it can be seen that BTO has been incorporated into the perovskite film; the XRD data of Fig. 4 proves that BTO has appeared in the composite film of Example 1; the JV test data of Fig. 5 shows that doped BTO The perovskite solar cell efficiency is 10.72%.
表1Table 1
实施例2Example 2
(1)钙钛矿层制备过程(1) Preparation process of perovskite layer
取PbI2、HC(NH2)2I放入烧杯中，加入无水级N-N二甲基甲酰胺和二甲基亚砜，温度为70℃，搅拌12小时，配制浓度为1.3mol/l的FAPbI3液体，取PbI2、CH3NH3I放入烧杯中，加入无水级N-N二甲基甲酰胺和二甲基亚砜，温度为70℃，搅拌12小时，配制浓度为1.3mol/l的MAPbI3液体，将上述溶液按体积比5:1混合，温度为70℃，搅拌12小时，配制(FAPbI3)0.83(MAPbI3)0.17溶液，把钛酸钡加入到上述溶液当中，钛酸钡的浓度为0.23mg/mL，将上述溶液滴加在处理好的介孔二氧化钛上，旋转涂膜，转速为1500r/min，旋涂时间30秒，将旋涂后的样品在150℃下，热处理30分钟。Take PbI 2 and HC(NH 2 ) 2 I into a beaker, add anhydrous grade NN dimethylformamide and dimethyl sulfoxide, and stir for 12 hours at a temperature of 70°C to prepare 1.3 mol/l FAPbI 3 liquid, take PbI 2 and CH 3 NH 3 I into a beaker, add anhydrous grade NN dimethylformamide and dimethyl sulfoxide, and stir for 12 hours at a temperature of 70°C to prepare a concentration of 1.3mol/ 1 of MAPbI 3 liquid, mix the above solution in a volume ratio of 5:1, the temperature is 70 ° C, stir for 12 hours, prepare a solution of (FAPbI 3 ) 0.83 (MAPbI 3 ) 0.17 , add barium titanate into the above solution, titanium The concentration of barium acid was 0.23 mg/mL, the above solution was added dropwise on the treated mesoporous titanium dioxide, and the film was spin-coated at a rotational speed of 1500 r/min, and the spin-coating time was 30 seconds. , heat treatment for 30 minutes.
总之，本发明通过在钙钛矿层中掺入具有铁电性的钛酸钡纳米颗粒，来改善钙钛矿太阳能电池中的铁电极化，提高钙钛矿太阳能电池的光电转换性能。本发明实验方法工艺简单，操作方便，成本低，制备温度低、薄膜形貌可控，适用于改善钙钛矿太阳能电池铁电极性，提高钙钛矿太阳能电池的稳定性和光电转化效率。In conclusion, the present invention improves the ferroelectric polarization in the perovskite solar cell by incorporating ferroelectric barium titanate nanoparticles into the perovskite layer, and improves the photoelectric conversion performance of the perovskite solar cell. The experimental method of the invention has the advantages of simple process, convenient operation, low cost, low preparation temperature and controllable film morphology, and is suitable for improving the ferroelectricity of the perovskite solar cell and improving the stability and photoelectric conversion efficiency of the perovskite solar cell.
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