CN114447228A - Perovskite solar cell with microcavity structure and preparation method thereof - Google Patents
Perovskite solar cell with microcavity structure and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种钙钛矿太阳能电池微腔的制备方法,通过ITO玻璃基片上方第一金属层,中部的钙钛矿介质,第一电荷传输层,第二电荷传输层以及第二金属层共同构成微腔;本发明提出的制备钙钛矿太阳能电池微腔的方法具有广泛的普适性,可以在金属层上方生长高质量的钙钛矿介质薄膜获得针对吸收边工作的谐振腔。本发明方法制备微腔的钙钛矿太阳能电池,其在长波的光场被调制增强,电流明显提升,并且可以极大降低其毒性。
The invention discloses a preparation method of a perovskite solar cell microcavity. The layers together constitute a microcavity; the method for preparing a perovskite solar cell microcavity proposed in the present invention has wide applicability, and a high-quality perovskite dielectric film can be grown on the metal layer to obtain a resonant cavity that operates on the absorption edge. The method of the present invention prepares a microcavity perovskite solar cell, which is modulated and enhanced in a long-wavelength light field, the current is significantly increased, and its toxicity can be greatly reduced.
Description
技术领域technical field
本发明涉及钙钛矿太阳能电池技术领域,尤其是一种具有微腔结构的钙钛矿太阳能电池及其制备方法。The invention relates to the technical field of perovskite solar cells, in particular to a perovskite solar cell with a microcavity structure and a preparation method thereof.
背景技术Background technique
钙钛矿太阳能电池(perovskite solar cell,PSC)是近年来发展的新型太阳能电池技术,其采用有机无机混合的铅卤钙钛矿材料作为光吸收层由于铅卤钙钛矿材料具有组分灵活、带隙可调、光吸收吸收高、载流子扩散距离长、载流子传输速率高等特点,吸引了光电子领域研究人员的广泛关注。其中,其带隙可根据组分的不同,从1.2~2.9eV连续可调的特性,更是使其在太阳能电池领域具有巨大的潜力。Perovskite solar cell (PSC) is a new type of solar cell technology developed in recent years, which uses organic-inorganic mixed lead-halide perovskite material as the light absorption layer. The characteristics of tunable band gap, high light absorption, long carrier diffusion distance, and high carrier transfer rate have attracted extensive attention of researchers in the field of optoelectronics. Among them, its band gap can be continuously adjusted from 1.2 to 2.9 eV according to different components, which makes it have great potential in the field of solar cells.
然而目前高效率的钙钛矿太阳能电池难以避免含铅原料的使用,一种主要的合理减毒方式是物理降铅,即减少含铅钙钛矿光吸收层的厚度。传统的钙钛矿光吸收层厚度为700~1000nm,理论计算已经证明钙钛矿光吸收层厚度最少只需200nm即可达到标准器件80%以上的效率,至少降低50%的毒性。然而,由于钙钛矿的吸收系数在短波长时极高,在长波长时较低,直接通过浓度调控和反溶剂时间调控减薄钙钛矿光吸收层厚度会使得长波部分(>700nm)的能量未被利用,使得器件效率难以进一步提升。在较为成熟的薄膜太阳能电池中(砷化镓电池,铜铟镓硒电池等),解决这类问题行之有效的方法是在太阳能电池中做出微腔,通过光场调控来提升长波的吸收。但对钙钛矿太阳能电池来说,由于基于溶液制备的特性,在金属层上涂覆钙钛矿光吸收层的质量受到界面性质的限制,同时对制备特定厚度的介质层也是不小的挑战。However, current high-efficiency perovskite solar cells are difficult to avoid the use of lead-containing raw materials. The thickness of the traditional perovskite light absorbing layer is 700-1000 nm. Theoretical calculations have proved that the perovskite light absorbing layer thickness of at least 200 nm can reach the efficiency of more than 80% of the standard device and reduce the toxicity by at least 50%. However, since the absorption coefficient of perovskite is extremely high at short wavelengths and low at long wavelengths, reducing the thickness of the perovskite light absorption layer directly through concentration regulation and anti-solvent time regulation will make the long-wavelength part (>700nm) thin. The energy is not utilized, making it difficult to further improve the device efficiency. In relatively mature thin-film solar cells (GaAs cells, Copper Indium Gallium Selenide cells, etc.), an effective way to solve such problems is to make a microcavity in the solar cell, and improve the long-wave absorption through light field regulation. . However, for perovskite solar cells, due to the characteristics of solution-based preparation, the quality of the perovskite light absorption layer coated on the metal layer is limited by the interface properties, and it is also a challenge to prepare a dielectric layer with a specific thickness. .
发明内容SUMMARY OF THE INVENTION
本发明所要解决的问题是:如何稳定的获得可工作的具有微腔结构的钙钛矿太阳能电池,如何提升微腔中介质的生长质量,以实现光场调控,进一步实现光吸收的增强。The problems to be solved by the present invention are: how to stably obtain a workable perovskite solar cell with a microcavity structure, and how to improve the growth quality of the medium in the microcavity, so as to realize the regulation of the light field and further realize the enhancement of light absorption.
为解决上述问题,本发明的技术方案为:For solving the above problems, the technical scheme of the present invention is:
一方面,本发明提供一种具有微腔结构的钙钛矿太阳能电池,包括依次层叠设置的衬底、透明导电层、第一电荷传输层、钙钛矿光吸收层、第二电荷传输层和第二金属层;其特点在于,在所述的透明导电层和第一电荷传输层之间还设有第一金属层,该第一金属层作为微腔入光端,所述的第二金属层作为微腔出光端。In one aspect, the present invention provides a perovskite solar cell with a microcavity structure, comprising a substrate, a transparent conductive layer, a first charge transport layer, a perovskite light absorption layer, a second charge transport layer and The second metal layer; it is characterized in that a first metal layer is further arranged between the transparent conductive layer and the first charge transport layer, the first metal layer serves as the light-inlet end of the microcavity, and the second metal layer is layer as the light-emitting end of the microcavity.
作为优选,所述透明导电层采用氧化铟锡ITO或氟掺杂氧化锡FTO材料中的一种,其厚度为100~600nm。Preferably, the transparent conductive layer is one of indium tin oxide (ITO) or fluorine-doped tin oxide (FTO) material, and its thickness is 100-600 nm.
作为优选,所述第一金属层为具有较强反射率和电导率的金属材料,金Au、银Ag、铜Cu中的一种,其厚度为5~15nm。Preferably, the first metal layer is a metal material with strong reflectivity and electrical conductivity, one of gold Au, silver Ag, and copper Cu, and the thickness thereof is 5-15 nm.
作为优选,步骤(1)所述的热处理温度为80~120℃,时间为1~5min;步骤(2)所述的热处理第一电荷传输层前驱体热处理温度为30~50℃。Preferably, the heat treatment temperature of the step (1) is 80-120°C, and the time is 1-5 minutes; the heat treatment temperature of the heat treatment of the first charge transport layer precursor described in the step (2) is 30-50°C.
作为优选,步骤(2)所述的热处理完成后与制备第一电荷传输层的时间间隔为0~3s。Preferably, the time interval between the completion of the heat treatment in step (2) and the preparation of the first charge transport layer is 0-3 s.
作为优选,第一电荷传输层与第二电荷传输层应具有不同电荷的传输特性,其中电子传输材料包括:采用二氧化钛TiO2、二氧化锡SnO2、氧化锌ZnO、C60溶液、[6,6]-苯基C61丁酸甲酯溶液中的任意一种,其厚度为20~120nm;空穴传输材料其采用三苯胺衍生物、2,2,7,7-四[N,N-二(4-甲氧基苯基)氨基]-9,9-螺二芴Spiro-OMeTAD、聚3,4-乙撑二氧噻吩:聚苯乙烯磺酸盐PEDOT:PSS、聚(3-己基噻吩)P3HT、2,3,5,6-四氟-7,7,8,8-四氰基二甲烷掺杂的聚三羧基胺PTAA:F4-TCNQ、聚[双(4-苯基)(2,4,6-三甲基苯基)胺]PTAA、硫氰酸亚铜CuSCN、氧化镍NiOx中的任意一种,其厚度为10~200nm。Preferably, the first charge transport layer and the second charge transport layer should have different charge transport properties, wherein the electron transport materials include: titanium dioxide TiO 2 , tin dioxide SnO 2 , zinc oxide ZnO, C 60 solution, [6, 6]-Any one of the methyl phenyl C 61 butyrate solution, the thickness of which is 20-120 nm; the hole transport material adopts triphenylamine derivatives, 2,2,7,7-tetrakis[N,N- Bis(4-methoxyphenyl)amino]-9,9-spirobifluorene Spiro-OMeTAD, poly3,4-ethylenedioxythiophene:polystyrenesulfonate PEDOT:PSS, poly(3-hexyl thiophene) P3HT, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanodimethane-doped polytricarboxyamine PTAA: F4-TCNQ, poly[bis(4-phenyl) (2,4,6-trimethylphenyl)amine] PTAA, any one of cuprous thiocyanate CuSCN, and nickel oxide NiO x , and the thickness thereof is 10 to 200 nm.
作为优选,所述钙钛矿光吸收层采用ABX3型三维钙钛矿,其分子式ABX3中的不同离子选用如下:正一价阳离子A,选用甲胺MA+、甲脒FA+、钾K+、铷Rb+、铯Cs+中的任意一种离子及任意几种离子的组合;正二价金属阳离子B,选用铅Pb2+、锗Ge2+、锡Sn2+中的任意一种离子及任意几种离子的组合;负一价阴离子X,选用氯Cl-、溴Br-、碘I-中的任意一种离子及任意几种离子的组合。Preferably, the perovskite light absorption layer adopts ABX 3 -type three-dimensional perovskite, and the different ions in its molecular formula ABX 3 are selected as follows: positive monovalent cation A, methylamine MA + , formamidine FA + , potassium K + , rubidium Rb + , cesium Cs + any one ion and any combination of several ions; positive divalent metal cation B, selects any one ion in lead Pb 2+ , germanium Ge 2+ , tin Sn 2+ and any combination of several ions; negative monovalent anion X, selects any one ion in chlorine Cl - , bromine Br - , iodine I - and any combination of several ions.
作为优选,所述钙钛矿光吸收层采用材料中的二维钙钛矿,其分子式L2An-1BnX3n+1或L2An-1BnX3n+1中的不同离子选用如下:正一价阳离子A、正二价金属阳离子B、负一价阴离子X这三种离子的选用与三维钙钛矿的选用相同;正一价有机阳离子A1,选用苯乙胺PEA+、丁胺BA+、乙胺EA+、二甲胺DMA+、甲基三乙基铵MTEA+、胍GA+、2-噻吩甲基铵ThMA+中的任意一种离子及任意几种离子的组合;正二价有机阳离子A2,选用3-氨甲基哌啶3AMP2+、4-氨甲基哌啶4AMP2+、3-氨甲基吡啶3AMPY2+、4-氨甲基吡啶4AMPY2+、乙二胺EDA2+、N,N-二甲基苯胺DPA2+、丙烷1,3-二铵PDA2+、1,4-丁二胺BDA2+、2,5-二氨甲基噻吩ThDMA2+、对亚二甲苯二胺PDMA2+、N,N-二甲基乙二胺DMEDA2+中的任意一种离子及任意几种离子的组合。Preferably, the perovskite light absorbing layer is a two-dimensional perovskite material whose molecular formula is L 2 A n-1 B n X 3n+1 or L 2 A n-1 B n X 3n+1 The selection of different ions is as follows: the selection of positive monovalent cation A, positive divalent metal cation B, and negative monovalent anion X is the same as the selection of three-dimensional perovskite; positive monovalent organic cation A 1 is selected from phenethylamine PEA + , butylamine BA + , ethylamine EA + , dimethylamine DMA + , methyltriethylammonium MTEA + , guanidine GA + , 2-thienylmethylammonium ThMA + , any ion and any kind of ions The combination; positive divalent organic cation A 2 , selects 3-aminomethylpiperidine 3AMP 2+ , 4-aminomethylpiperidine 4AMP 2+ , 3-aminomethyl pyridine 3AMPY 2+ , 4-aminomethyl pyridine 4AMPY 2+ , ethylenediamine EDA 2+ , N,N-dimethylaniline DPA 2+ ,
作为优选,第二金属层,其采用金Au、银Ag、铜Cu中的一种,其厚度为90~300nm。Preferably, the second metal layer is one of gold Au, silver Ag, and copper Cu, and the thickness thereof is 90-300 nm.
另一方面,本发明还提供一种具有微腔结构的钙钛矿太阳能电池的制备方法,包括步骤:On the other hand, the present invention also provides a method for preparing a perovskite solar cell with a microcavity structure, comprising the steps of:
(1)在透明导电层上制备第一金属层,作为微腔入光端,并进行热处理,使第一金属层和透明导电层处于微热状态;(1) Prepare a first metal layer on the transparent conductive layer, as the light-inlet end of the microcavity, and perform heat treatment to make the first metal layer and the transparent conductive layer in a microthermal state;
(2)热处理第一电荷传输层前驱体,并将微热的第一电荷传输层制备在第一金属层上,后进行退火处理;(2) heat treating the first charge transport layer precursor, and preparing the first charge transport layer with slight heat on the first metal layer, and then performing annealing treatment;
(3)在第一电荷传输层上制备钙钛矿光吸收层,进行退火处理;(3) preparing a perovskite light absorption layer on the first charge transport layer, and performing annealing treatment;
(4)在钙钛矿光吸收层上制备第二电荷传输层后,进行退火处理;(4) after preparing the second charge transport layer on the perovskite light absorption layer, annealing treatment is performed;
(5)在第二电荷传输层上制备第二金属层,作为微腔出光端和电极。(5) A second metal layer is prepared on the second charge transport layer to serve as the light-emitting end and electrode of the microcavity.
与现有技术相比,本发明的优点在于:Compared with the prior art, the advantages of the present invention are:
一、由于采用第一金属层作为光入射端和反射端,第二金属层作为光反射端,使光在腔体内发生谐振,产生场增强效应,从而降低了光能的损耗。1. Because the first metal layer is used as the light incident end and the reflection end, and the second metal layer is used as the light reflection end, the light resonates in the cavity, resulting in a field enhancement effect, thereby reducing the loss of light energy.
二、由于对第一金属层和第一电荷传输层进行热处理,降低了薄膜间的应力,所生长的钙钛矿光吸收层具有成膜质量高,薄膜缺陷密度小,表面粗糙度低的特点,极大的提升了具有微腔结构钙钛矿太阳能电池的效率。2. Due to the heat treatment of the first metal layer and the first charge transport layer, the stress between the films is reduced, and the grown perovskite light absorption layer has the characteristics of high film formation quality, low film defect density and low surface roughness. , which greatly improves the efficiency of perovskite solar cells with microcavity structure.
三、本发明所涉及的薄膜谐振腔制备工艺该工艺具有广泛的普适性,适用于各种类型的太阳能电池制备工艺,能很好地适配工业化湿法制膜流程,具有极大的商业化价值;3. The preparation process of the thin film resonant cavity involved in the present invention has a wide range of applicability, is suitable for various types of solar cell preparation processes, can be well adapted to the industrial wet film preparation process, and has great commercialization. value;
四、本发明所制备的PSC在全波长具有极高的光吸收率和效率,同时毒性比常规PSC低40%以上。该发明能极大的推动PSC在商业化的应用,使得毒性达到各种环保标准。Fourth, the PSC prepared by the present invention has extremely high light absorption rate and efficiency at all wavelengths, and at the same time, the toxicity is more than 40% lower than that of the conventional PSC. The invention can greatly promote the commercial application of PSC, so that the toxicity can meet various environmental protection standards.
附图说明Description of drawings
图1是本发明涉及的钙钛矿太阳能电池微腔制备工艺的流程示意图。FIG. 1 is a schematic flow chart of the preparation process of the perovskite solar cell microcavity involved in the present invention.
图2是本发明所制备的器件结构示意图。FIG. 2 is a schematic diagram of the structure of the device prepared by the present invention.
图中:衬底(1)、透明导电层(2)、第一金属层(3)、第一电荷传输层(4)、钙钛矿光吸收层(5)、第二电荷传输层(6)、第二金属层(7)。In the figure: substrate (1), transparent conductive layer (2), first metal layer (3), first charge transport layer (4), perovskite light absorption layer (5), second charge transport layer (6) ), the second metal layer (7).
具体实施方式:Detailed ways:
下面结合附图及实施例对本发明作进一步说明。The present invention will be further described below with reference to the accompanying drawings and embodiments.
实施例1:将衬底及透明导电层组成的基板进行常规溶剂清洗,随后紫外臭氧处理15min,在基板上制备Cu第一金属层(蒸镀,10nm),在热台上微热PTAA空穴传输层溶液(热台温度40℃,加热5min),将含金属层的基片在热台上加热(热台温度40℃,加热3min),在其上制备PTAA空穴传输层(旋涂2000rpm,30s)并退火10min获得10nm厚度的PTAA。将钙钛矿前驱体溶液沉积于PTAA层之上(旋涂4000rpm,60s,45s时滴加氯苯)。将薄膜转移至热台上(热台温度100℃)将钙钛矿薄膜热退火20min,最终获得厚度为400nm的钙钛矿薄膜。冷却薄膜至常温,并蒸镀C60电子传输层40nm,蒸镀Cu第二金属层90nm。所制备的PSC的VOC=1.03V,JSC=22.13mA/cm2,FF=0.75,PCE=17.2%,750nm光振幅增强3.3倍,650nm以上光吸收率均达到85%以上,达到相同功率毒性降低33%。Example 1: The substrate composed of the substrate and the transparent conductive layer was cleaned with a conventional solvent, followed by ultraviolet ozone treatment for 15 minutes, and the first metal layer of Cu (evaporation, 10 nm) was prepared on the substrate, and the PTAA holes were slightly heated on the hot stage. Transport layer solution (hot stage temperature 40°C, heating for 5min), the substrate containing the metal layer was heated on the hot stage (hot stage temperature 40°C, heating 3min), on which a PTAA hole transport layer was prepared (spin coating 2000rpm) , 30 s) and annealed for 10 min to obtain PTAA with a thickness of 10 nm. The perovskite precursor solution was deposited on top of the PTAA layer (spin coating at 4000 rpm, 60 s, dropwise addition of chlorobenzene at 45 s). The film was transferred to a hot stage (the temperature of the hot stage was 100 °C), and the perovskite film was thermally annealed for 20 min, and finally a perovskite film with a thickness of 400 nm was obtained. The film was cooled to room temperature, and a C 60 electron transport layer of 40 nm was evaporated, and a Cu second metal layer of 90 nm was evaporated. The prepared PSC has V OC =1.03V, J SC =22.13mA/cm 2 , FF=0.75, PCE=17.2%, the 750nm light amplitude is enhanced by 3.3 times, the light absorption rate above 650nm is above 85%, and the same power is achieved Toxicity reduced by 33%.
实施例2:将衬底及透明导电层组成的基板进行常规溶剂清洗,随后紫外臭氧处理15min,在基板上制备Au第一金属层(蒸镀,10nm),在热台上微热PTAA空穴传输层溶液(热台温度40℃,加热5min),将含金属层的基片在热台上加热(热台温度40℃,加热3min),在其上制备PTAA空穴传输层(旋涂2000rpm,30s)并退火10min获得10nm厚度的PTAA。将钙钛矿前驱体溶液沉积于PTAA层之上(旋涂4000rpm,60s,45s时滴加氯苯)。将薄膜转移至热台上(热台温度100℃)将钙钛矿薄膜热退火20min,最终获得厚度为410nm的钙钛矿薄膜。冷却薄膜至常温,并蒸镀C60电子传输层40nm,蒸镀Cu第二金属层90nm。所制备的PSC的VOC=1.01V,JSC=21.53mA/cm2,FF=0.76,PCE=16.67%,750nm光振幅增强3.1倍,650nm以上光吸收率均达到84%以上,达到相同功率毒性降低31%。Example 2: The substrate composed of the substrate and the transparent conductive layer was cleaned with a conventional solvent, followed by ultraviolet ozone treatment for 15 minutes, and the Au first metal layer (evaporation, 10 nm) was prepared on the substrate, and the PTAA holes were slightly heated on the hot stage. Transport layer solution (hot stage temperature 40°C, heating for 5min), the substrate containing the metal layer was heated on the hot stage (hot stage temperature 40°C, heating 3min), on which a PTAA hole transport layer was prepared (spin coating 2000rpm) , 30 s) and annealed for 10 min to obtain PTAA with a thickness of 10 nm. The perovskite precursor solution was deposited on top of the PTAA layer (spin coating at 4000 rpm, 60 s, dropwise addition of chlorobenzene at 45 s). The film was transferred to a hot stage (the temperature of the hot stage was 100 °C), and the perovskite film was thermally annealed for 20 min, and finally a perovskite film with a thickness of 410 nm was obtained. The film was cooled to room temperature, and a C 60 electron transport layer of 40 nm was evaporated, and a Cu second metal layer of 90 nm was evaporated. The prepared PSC has V OC =1.01V, J SC =21.53mA/cm2, FF=0.76, PCE=16.67%, the 750nm light amplitude is enhanced by 3.1 times, and the light absorption rate above 650nm is above 84%, achieving the same power toxicity 31% lower.
实施例3:将衬底及透明导电层组成的基板进行常规溶剂清洗,随后紫外臭氧处理15min,在基板上制备Cu第一金属层(蒸镀,10nm),在热台上微热PTAA空穴传输层溶液(热台温度40℃,加热5min),将含金属层的基片在热台上加热(热台温度40℃,加热3min),在其上制备PTAA空穴传输层(旋涂2000rpm,30s)并退火10min获得10nm厚度的PTAA。将钙钛矿前驱体溶液沉积于PTAA层之上(旋涂4000rpm,60s,45s时滴加氯苯)。将薄膜转移至热台上(热台温度100℃)将钙钛矿薄膜热退火20min,最终获得厚度为410nm的钙钛矿薄膜。冷却薄膜至常温,并蒸镀C60电子传输层40nm,蒸镀Cu第二金属层90nm。所制备的PSC的VOC=1.04V,JSC=22.03mA/cm2,FF=0.74,PCE=17.09%,750nm光振幅增强3.2倍,650nm以上光吸收率均达到84%以上,达到相同功率毒性降低33%。Example 3: The substrate composed of the substrate and the transparent conductive layer was cleaned with a conventional solvent, followed by ultraviolet ozone treatment for 15 minutes, and the first metal layer of Cu (evaporation, 10 nm) was prepared on the substrate, and the PTAA holes were slightly heated on the hot stage. Transport layer solution (hot stage temperature 40°C, heating for 5min), the substrate containing the metal layer was heated on the hot stage (hot stage temperature 40°C, heating 3min), on which a PTAA hole transport layer was prepared (spin coating 2000rpm) , 30 s) and annealed for 10 min to obtain PTAA with a thickness of 10 nm. The perovskite precursor solution was deposited on top of the PTAA layer (spin coating at 4000rpm, 60s, dropwise addition of chlorobenzene at 45s). The film was transferred to a hot stage (the temperature of the hot stage was 100 °C), and the perovskite film was thermally annealed for 20 min, and finally a perovskite film with a thickness of 410 nm was obtained. The film was cooled to room temperature, and a C 60 electron transport layer of 40 nm was evaporated, and a Cu second metal layer of 90 nm was evaporated. The prepared PSC has V OC =1.04V, J SC =22.03mA/cm2, FF=0.74, PCE=17.09%, the 750nm light amplitude is enhanced by 3.2 times, and the light absorption rate above 650nm is above 84%, achieving the same power toxicity 33% lower.
实施例4:将衬底及透明导电层组成的基板进行常规溶剂清洗,随后紫外臭氧处理15min,在基板上制备Cu第一金属层(蒸镀,10nm),在热台上微热PTAA空穴传输层溶液(热台温度40℃,加热5min),将含金属层的基片在热台上加热(热台温度40℃,加热3min),在其上制备PTAA空穴传输层(旋涂2000rpm,30s)并退火10min获得10nm厚度的PTAA。将钙钛矿前驱体溶液沉积于PTAA层之上(旋涂4000rpm,60s,45s时滴加氯苯)。将薄膜转移至热台上(热台温度100℃)将钙钛矿薄膜热退火20min,最终获得厚度为410nm的钙钛矿薄膜。冷却薄膜至常温,并蒸镀C60电子传输层40nm,蒸镀Cu第二金属层90nm。所制备的PSC的VOC=1.03V,JSC=22.03mA/cm2,FF=0.76,PCE=17.57%,750nm光振幅增强3.3倍,650nm以上光吸收率均达到85%以上,达到相同功率毒性降低34%。Example 4: The substrate composed of the substrate and the transparent conductive layer was cleaned with a conventional solvent, followed by ultraviolet ozone treatment for 15 minutes, and the first metal layer of Cu (evaporation, 10 nm) was prepared on the substrate, and the PTAA holes were slightly heated on the hot stage. Transport layer solution (hot stage temperature 40°C, heating for 5min), the substrate containing the metal layer was heated on the hot stage (hot stage temperature 40°C, heating 3min), on which a PTAA hole transport layer was prepared (spin coating 2000rpm) , 30 s) and annealed for 10 min to obtain PTAA with a thickness of 10 nm. The perovskite precursor solution was deposited on top of the PTAA layer (spin coating at 4000 rpm, 60 s, dropwise addition of chlorobenzene at 45 s). The film was transferred to a hot stage (the temperature of the hot stage was 100 °C), and the perovskite film was thermally annealed for 20 min, and finally a perovskite film with a thickness of 410 nm was obtained. The film was cooled to room temperature, and a C 60 electron transport layer of 40 nm was evaporated, and a Cu second metal layer of 90 nm was evaporated. The prepared PSC has V OC =1.03V, J SC =22.03mA/cm2, FF = 0.76, PCE = 17.57%, the 750nm light amplitude is enhanced by 3.3 times, the light absorption above 650nm is above 85%, and the same power toxicity is achieved. 34% lower.
实施例5:将衬底及透明导电层组成的基板进行常规溶剂清洗,随后紫外臭氧处理15min,在基板上制备Cu第一金属层(蒸镀,10nm),在热台上微热PTAA空穴传输层溶液(热台温度40℃,加热5min),将含金属层的基片在热台上加热(热台温度40℃,加热3min),在其上制备PTAA空穴传输层(旋涂2000rpm,30s)并退火10min获得10nm厚度的PTAA。将钙钛矿前驱体溶液沉积于PTAA层之上(旋涂4000rpm,60s,45s时滴加氯苯)。将薄膜转移至热台上(热台温度100℃)将钙钛矿薄膜热退火20min,最终获得厚度为410nm的钙钛矿薄膜。冷却薄膜至常温,并蒸镀C60电子传输层40nm,蒸镀Cu第二金属层90nm。所制备的PSC的VOC=1.02V,JSC=21.73mA/cm2,FF=0.76,PCE=16.94%,750nm光振幅增强3.2倍,650nm以上光吸收率均达到84%以上,达到相同功率毒性降低32%。Example 5: The substrate composed of the substrate and the transparent conductive layer was cleaned with a conventional solvent, followed by ultraviolet ozone treatment for 15 minutes, and the first metal layer of Cu (evaporation, 10 nm) was prepared on the substrate, and the PTAA holes were slightly heated on the hot stage. Transport layer solution (hot stage temperature 40°C, heating for 5min), the substrate containing the metal layer was heated on the hot stage (hot stage temperature 40°C, heating 3min), on which a PTAA hole transport layer was prepared (spin coating 2000rpm) , 30 s) and annealed for 10 min to obtain PTAA with a thickness of 10 nm. The perovskite precursor solution was deposited on top of the PTAA layer (spin coating at 4000 rpm, 60 s, dropwise addition of chlorobenzene at 45 s). The film was transferred to a hot stage (the temperature of the hot stage was 100 °C), and the perovskite film was thermally annealed for 20 min, and finally a perovskite film with a thickness of 410 nm was obtained. The film was cooled to room temperature, and a C 60 electron transport layer of 40 nm was evaporated, and a Cu second metal layer of 90 nm was evaporated. The prepared PSC has V OC =1.02V, J SC =21.73mA/cm2, FF=0.76, PCE=16.94%, the 750nm light amplitude is enhanced by 3.2 times, and the light absorption rate above 650nm is above 84%, achieving the same power toxicity 32% lower.
本发明已经通过上述实施例进行了说明,但应当理解的是,上述实施例只是用于举例和说明的目的,而非意在将本发明限制于所描述的实施例范围内。此外本领域技术人员可以理解的是,本发明并不局限于上述实施例,根据本发明的教导还可以做出更多种的变型和修改,这些变型和修改均落在本发明所要求保护的范围以内。本发明的保护范围由附属的权利要求书及其等效范围所界定。The present invention has been described by the above-mentioned embodiments, but it should be understood that the above-mentioned embodiments are only for the purpose of illustration and description, and are not intended to limit the present invention to the scope of the described embodiments. In addition, those skilled in the art can understand that the present invention is not limited to the above-mentioned embodiments, and more variations and modifications can also be made according to the teachings of the present invention, and these variations and modifications all fall within the protection claimed in the present invention. within the range. The protection scope of the present invention is defined by the appended claims and their equivalents.
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