WO2020029205A1 - 基于梯度退火与反溶剂协同效应制备无机钙钛矿电池的方法及制备的无机钙钛矿电池 - Google Patents

基于梯度退火与反溶剂协同效应制备无机钙钛矿电池的方法及制备的无机钙钛矿电池 Download PDF

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WO2020029205A1
WO2020029205A1 PCT/CN2018/099716 CN2018099716W WO2020029205A1 WO 2020029205 A1 WO2020029205 A1 WO 2020029205A1 CN 2018099716 W CN2018099716 W CN 2018099716W WO 2020029205 A1 WO2020029205 A1 WO 2020029205A1
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perovskite
preparing
transport layer
antisolvent
electrode
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李耀文
陈炜杰
李永舫
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Suzhou University
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Definitions

  • the invention relates to a solar cell, in particular to an all-inorganic perovskite solar cell and a preparation method thereof, in particular to a method for preparing an inorganic perovskite battery based on the synergistic effect of gradient annealing and antisolvent, and the prepared inorganic perovskite battery .
  • Inorganic perovskite solar cells use a laminated structure, placing the inorganic perovskite active layer between the electron transport layer and the hole transport layer, avoiding the direct contact of perovskite with the anode and the cathode to reduce the solar energy conversion efficiency.
  • small organic molecules or polymers are used as the material of the hole transport layer, and metal oxides are used as the material of the electron transport layer.
  • the film formation quality of the perovskite active layer plays a vital role in the photoelectric conversion efficiency of solar cells.
  • the main method for preparing inorganic perovskites is solution film formation.
  • the solution film formation method generally requires an antisolvent to accelerate the precipitation of crystals.
  • the currently used anti-solvents are usually toxic solvents such as chlorobenzene and chloroform, not green solvents, which will have a great impact on the environment; in addition, small grains in inorganic perovskite films And the porous morphology will reduce the overall performance of the battery.
  • the purpose of the present invention is to provide an all-inorganic perovskite solar cell and a preparation method thereof.
  • the method of gradient annealing and green anti-solvent is used to effectively improve the photoelectric conversion efficiency of the solar cell. Easy to operate.
  • a method for preparing an inorganic perovskite battery based on the synergistic effect of gradient annealing and an antisolvent and a method of preparing a perovskite layer by a method of gradient annealing and antisolvent treatment.
  • the thickness of the perovskite layer is 100-1000 nm; in the perovskite precursor solution for preparing the perovskite layer, the solvent is an amide solvent and / or a sulfone solvent, preferably DMF and / or DMSO, and more preferably DMSO; the concentration of the perovskite precursor solution for preparing the perovskite layer is 0.4 to 2M, preferably 1 to 1.8M; the gradient annealing process is 40 to 70 ° C / 0.5 to 5min + 70 to 130 ° C / 0.5 to 5min + 130 ⁇ 160 °C / 5 ⁇ 20min + 160 ⁇ 280 °C / 0 ⁇ 20mi, preferably, the gradient annealing process is 40 ⁇ 60 °C / 1 ⁇ 2min + 80 ⁇ 120 °C / 1 ⁇ 2min + 150 ⁇ 180 °C / 5 ⁇ 15min + 180 ⁇ 200 °C / 0
  • a precursor solution with a lower concentration (less than 0.8 M) and a mixed solvent containing a large amount of DMF are generally used.
  • the existing method is generally accompanied by Low rotation speed, less than 1500 rpm, so there is no guarantee of film formation quality; the present invention uses pure DMSO as a solvent to ensure a high concentration precursor solution.
  • high-speed spin coating (3000 rpm) a high-quality film (surface flatness) is obtained Uniformity, good stability, good repeatability, and fewer defects), and the film thickness can reach 500nm, which has achieved unexpected technical effects.
  • the invention adopts the method of gradient annealing and green antisolvent for the first time to prepare an inorganic perovskite layer on the electron (hole) transport layer.
  • the prepared inorganic perovskite active layer has a flat and uniform surface, large grains, and few grain boundaries. Good stability and reproducibility, no need for toxic solvents; especially the inorganic perovskite prepared by the present invention has extremely strong crystalline strength, which makes the perovskite molecular orientation extremely high and the film quality high. High photoelectric conversion efficiency.
  • a method for preparing a perovskite thin film for an inorganic perovskite battery includes the following steps:
  • a method of gradient annealing and anti-solvent treatment is used to prepare a perovskite film on the hole transport layer.
  • the inorganic perovskite thin film prepared by the gradient annealing and the green anti-solvent method of the present invention has greatly improved the film formation uniformity and flatness, and the efficiency and stability of the device have been further improved.
  • Wide band gap inorganic perovskite battery (680nm absorption edge) not only guarantees high photoelectric conversion efficiency, but also provides important help for the development of translucent batteries and laminated batteries.
  • the transparent substrate is one of a glass substrate, a quartz substrate, a PET plastic substrate, a PEN plastic substrate, and a flexible grid silver substrate;
  • the cathode is indium tin oxide or fluorine-doped tin dioxide;
  • the anode is indium tin oxide or fluorine-doped tin dioxide;
  • the cathode or anode is prepared on a transparent substrate by a magnetron sputtering method;
  • the material of the electron transport layer is ZnO, TiO 2 , SnO 2 , PCBM, fullerene, One or more of the fullerene derivatives;
  • the material of the hole transport layer is selected from poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine], poly3, 4-ethylenedioxythiophene / polystyrenesulfonate, nickel oxide, copper oxide, 2,2 ', 7,7'-tetrakis [N, N-bis (4-me
  • conductive glass coated with an indium tin oxide film can be used as the cathode / anode of the battery; fluorine-doped SnO 2 conductive glass, commonly known as FTO, can be used as the cathode / anode.
  • the electron transport layer in the nip structure is a metal oxide such as ZnO, TiO 2 , SnO 2 or a metal-oxidized composite transport layer, a fullerene such as PCBM, C 60 and One or more of a fullerene derivative and an organic-inorganic hybrid electron-transporting layer; an electron-transporting layer is prepared on the cathode by annealing after spin coating, and the spin coating speed is 1000-5000 rpm and the time is 10 ⁇ 60s, thickness is 10 ⁇ 100nm, annealing temperature is 100 ⁇ 300 °C, and time is 10 ⁇ 60min.
  • a metal oxide such as ZnO, TiO 2 , SnO 2 or a metal-oxidized composite transport layer
  • a fullerene such as PCBM, C 60 and One or more of a fullerene derivative and an organic-inorganic hybrid electron-transporting layer
  • an electron-transporting layer is prepared on the cathode by annealing after spin coating,
  • the pin-type hole transport layer is selected from polymers having a triphenylamine structure such as poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine], and poly3,4-ethylene
  • a combination of p-type semiconductors such as dioxythiophene / polystyrene sulfonate and organic salts; one of metal oxides such as nickel oxide and copper oxide;
  • a hole-transporting layer is prepared on the perovskite layer by a spin coating method The speed of the spin coating is 1000 to 6000 rpm, the time is 20 to 60 s, and the thickness is 5 to 200 nm.
  • the hole transport layer of the pin structure is selected from poly [bis (4-phenyl) (2,4,6) -Trimethylphenyl) amine] and other polymers with a triphenylamine structure, a combination of p-type semiconductors such as poly3,4-ethylenedioxythiophene / polystyrene sulfonate and organic salts, nickel oxide, copper oxide
  • a spin-coating method is used to prepare a hole transport layer on the anode. The spin-coating speed is 1000 to 6000 rpm, the time is 20 to 60 s, and the thickness is 5 to 200 nm.
  • the hole transporting layer of the nip type structure is selected from 2,2 ', 7,7'-tetrakis [N, N-bis (4-methoxyphenyl) amino] -9,9'-spirobifluorene-based small molecules, poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] and other triphenylamine structural compounds, cuprous thiocyanate, oxidation
  • metal oxides such as nickel, copper oxide, and molybdenum oxide
  • a hole transport layer is prepared on the perovskite layer by a spin coating method, the spin coating speed is 1000 to 6000 rpm, the time is 20 to 60 s, and the thickness is It is 50 to 300 nm.
  • the electron-transporting layer described in the p-i-n-type structure includes metal oxides such as ZnO, fullerenes and fullerene derivatives such as PCBM, and composite electron-transporting layers of inorganic oxides and organics.
  • the spin-coating method is used to prepare an electron transport layer on the anode.
  • the spin-coating speed is 1000 to 5000 rpm, the time is 10 to 60 s, the thickness is 10 to 100 nm, the annealing temperature is 100 to 300 ° C, and the time is 10 ⁇ 60min.
  • the electron transport layer described in the p-i-n structure includes metal oxides such as ZnO, fullerenes and fullerene derivatives such as PCBM, and composite electron transport layers of inorganic oxides and organics.
  • the spin-coating method is used to prepare an electron transport layer on the perovskite layer.
  • the spin-coating speed is 1000 to 5000 rpm, the time is 10 to 60 s, the thickness is 10 to 100 nm, and the annealing temperature is 100 to 300 ° C. It is 10 ⁇ 60min.
  • the electrode is one or more of an Au electrode, an Ag electrode, an Al electrode, a Cu electrode, a carbon electrode, a PH1000 polymer electrode, and a metal oxide electrode.
  • an electrode is prepared on the hole (or electron) transport layer by a method of evaporation or transfer; the thickness of the electrode is 10 to 200 nm; and the electrode is an Au electrode or an Ag electrode.
  • highly conductive metal or composite metal electrode such as Al electrode, Cu electrode, carbon electrode, polymer electrode such as PH1000, and metal oxide electrode.
  • the perovskite solar cell of the invention has the advantages of high efficiency, low cost, and convenient preparation.
  • the perovskite material has better light absorption, longer carrier transmission distance, weaker exciton binding energy and The characteristics of very few surface defects make it a very competitive material, which has a broad application prospect in the field of batteries and luminescence.
  • the all-inorganic perovskite film disclosed in the present invention has a qualitative improvement in thermal stability, and the inorganic perovskite film does not decompose at about 300 ° C.
  • the development of batteries and laminated batteries has provided important help. In combination with organic solar cells, perovskite batteries, silicon batteries, and CIGS batteries, the efficiency of laminated batteries can be effectively improved.
  • the present invention chooses to prepare the perovskite layer by means of gradient annealing and anti-solvent.
  • the surface of the obtained perovskite film is uniform, stable, repeatable, with fewer defects and high photoelectric conversion efficiency; and high-quality inorganic Perovskite films also have good application prospects in the LED field;
  • the present invention utilizes a green anti-solvent, abandons the traditional toxic anti-solvent, and effectively reduces environmental pollution;
  • the wide band gap inorganic perovskite solar cell prepared by the present invention has a wide band gap, has a very high utilization rate of light before 680 nm, and its narrow absorption is expected to be used as a bottom battery for a laminated battery, improving the laminated battery.
  • FIG. 1 is a photo of direct high temperature annealing and gradient annealing of CsPbI 2 Br in Example 1;
  • Example 2 is a SEM image of CsPbI 2 Br direct high temperature annealing and gradient annealing in Example 1;
  • Example 3 is a SEM cross-sectional view of a CsPbI 2 Br perovskite layer in Example 1, which is Glass / ITO / TiO 2 / CsPbI 2 Br / Spiro-OMeTAD / Au from bottom to top;
  • Example 4 is a JV curve diagram of direct high-temperature annealing and gradient annealing of a CsPbI 2 Br perovskite battery in Example 1;
  • FIG. 6 is a color change diagram of gradient annealing of a CsPbI 2 Br perovskite layer in Example 2 after different antisolvent treatments;
  • Example 7 is a SEM image of a CsPbI 2 Br film treated with different antisolvents in Example 2 after annealing at 50 ° C. for 1 minute;
  • Example 8 is a comparison of an optical microscope image and an SEM image of a fringe CsPbI 2 Br perovskite thin film edge and a center in Example 2;
  • Example 10 is a SEM image of a CsPbI 2 Br film treated with different antisolvents in Example 2 ;
  • Example 11 is a JV curve diagram of a CsPbI 2 Br device treated with different anti-solvents in Example 2 ;
  • FIG. 12 is a simulation diagram of the synergistic effect of gradient annealing and antisolvent in the second embodiment
  • FIG. 13 shows the humidity stability of the CsPbI 2 Br device under the synergistic effect of gradient annealing and antisolvent in Example 2.
  • a glass rigid substrate is used for polishing, and then a layer of indium tin oxide film is plated on the glass by a magnetron sputtering method to form an ITO conductive glass as a cathode of a solar cell;
  • the spin-coated with an ITO electron transport layer was spin-coated was placed in a nitrogen glove box the perovskite precursor solution, the solution is divided into groups PbI 2, CsI, and PbBr 2, the composition at a concentration of 2 Br CsPbI 1.3M solution of
  • the solvent is pure DMSO; the precursor solution can be used after stirring for two hours and filtered; the spin coating rate is 3000 rpm and the time is 30s.
  • gradient annealing is performed, first annealing at 50 ° C for 1 minute, and then at 100 ° C.
  • Figure 1 shows a direct one-step high-temperature annealing (160 ° C / 10min or 100 ° C / 12min) and gradient annealing. (50 °C / 1min + 100 °C / 1min + 160 °C / 10min) photos of inorganic perovskite films, it can be seen from the figure that the surface of the film directly annealed at high temperature is very rough, while the surface of the gradient annealed film is smoother, which illustrates the gradient annealing Importance for improving film quality;
  • FIG. 2 is a scanning electron microscope (SEM) image of an inorganic perovskite thin film directly subjected to one-step high-temperature annealing and gradient annealing. As can be seen from the figure, the film coverage of direct high-temperature annealing is low, while the film coverage of gradient annealing is high. Good film formation;
  • the oxidized hole-transport layer is placed in a coating machine to vapor-deposit an Au electrode with a thickness of 80 nm.
  • the CsPbI 2 Br perovskite battery has been prepared.
  • the structure is shown in Figure 3.
  • the blank indicates no antisolvent treatment, and the toluene and isopropanol indicate that they have been treated with toluene and isopropanol, respectively. It can be seen that the perovskite
  • the film thickness is 500 nm.
  • Figure 4 and Table 1 are the efficiency table and JV curve chart of direct high temperature annealing (160 ° C / 10min) and gradient annealing of perovskite cells of CsPbI 2 Br. It can be seen that the film forming properties of the thin film directly annealed at a high temperature are extremely poor, so the performance parameters of the battery are not good, which is mainly due to the direct contact between the upper and lower transport layers caused by the poor film coverage of the perovskite. The performance of the gradient-annealed perovskite battery is superior, which is comparable to the highest efficiency of the inorganic perovskite battery reported; the PCE of the battery after direct high temperature annealing at 100 ° C is 3.49%.
  • a glass rigid substrate is used for polishing, and then a layer of indium tin oxide film is plated on the glass by a magnetron sputtering method to form an ITO conductive glass as a cathode of a solar cell;
  • the spin-coated with an ITO electron transport layer was spin-coated was placed in a nitrogen glove box the perovskite precursor solution, the solution is divided into groups PbI 2, CsI, and PbBr 2, the composition at a concentration of 2 Br CsPbI 1.3M solution of ;
  • the solvent is pure DMSO; the precursor solution is stirred for two hours and then filtered and used.
  • the spin coating rate was 3000 rpm and the time was 30 s.
  • 150 ⁇ l of isopropyl alcohol or toluene solution was added dropwise. After the spin coating was completed, gradient annealing was performed.
  • the film was annealed at 50 ° C for 1 minute, and then at 100 ° C Annealed for 1 minute, and finally annealed at 160 ° C for 10 minutes to obtain an inorganic perovskite film. It is worth mentioning that if there is no gradient annealing process, the solution is annealed at 100 ° C or higher directly after the antisolvent is added dropwise.
  • the SEM image is shown in Figure 5. The grains cannot completely cover the entire film, and the pores are large. This is similar to the SEM morphology of direct high temperature annealing without the addition of an anti-solvent.
  • the PCE for preparing the battery is 5.73%. If 80 ° C / 1min + is selected At 120 ° C / 8min, the PCE of the battery was 6.83%; this further proves the importance of the gradient annealing of the present invention to the film quality.
  • the influence is great; compared to the center of the blank film, the optical microscope and SEM images show a denser film; and the film treated with toluene or isopropanol is more uniform during the first annealing (especially isopropanol). ), The resulting film has a smaller surface roughness, and the entire film is very uniform, and the edges have no white uneven stripes, which provides a guarantee for high-performance devices.
  • Figure 9 is an image of the specular reflection of the isopropanol-treated film, which fully illustrates the uniformity and flatness of the film;
  • Figure 10 is a SEM image of the film treated with different anti-solvents. Grade-sized grains are far superior to perovskite films without anti-solvent treatment or toluene treatment. This is also the reason for the excellent performance of isopropanol-treated devices.
  • Related device parameters and JV curves are shown in Table 2 and Figure 11.
  • a simulated plot of gradient annealing and antisolvent synergy is shown in Figure 12.
  • the present invention can use a high-concentration precursor solution and a high rotation speed to obtain a high-thickness, high-quality perovskite film, which overcomes the technical defects of the prior art that a thin film with a high thickness can be obtained at a low rotation speed and solves the problem.
  • the existing perovskite film has many technical defects such as more pores and smaller grains, and has achieved unexpected technical effects.
  • the perovskite film is placed on a vacuum chuck, and the Spiro-OMeTAD hole transport layer is spin-coated at a speed of 3000 rpm and 30 s, and oxidized in dry air for 12 hours to obtain a hole transport layer with a thickness of 150 nm;
  • the crystal quality of the thin films treated with different anti-solvents is inconsistent, resulting in different device stability, as shown in Figure 13.
  • the IPA-treated device can maintain 95% of the initial efficiency
  • the toluene-treated device can maintain 70% of the initial efficiency
  • the blank device efficiency decays to 56% of the initial efficiency.
  • the quality of the crystal has a great impact on the stability of the device, and larger grains with fewer defect states help to suppress the degradation of the thin film itself, so that the device performance remains stable.
  • the concentration and composition of the precursor solution can be adjusted, and details are not described herein.
  • the invention adopts gradient annealing and green anti-solvent to treat the inorganic perovskite thin film to obtain a thin film with larger crystal grains, higher purity and better stability.
  • the inorganic perovskite film prepared by this method has good thermal stability, does not degrade at high temperature, and has good stability at lower humidity; and the efficiency of the inorganic perovskite battery prepared by this method It has exceeded 16% and is the highest efficiency in the field of inorganic perovskite.

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Abstract

本发明公开了一种基于梯度退火与反溶剂协同效应制备无机钙钛矿电池的方法及制备的无机钙钛矿电池，是一种能够在低温下完成、制备简易、成本较低以及效率较高的钙钛矿太阳能电池，其中，钙钛矿层选择利用梯度退火以及反溶剂处理的溶液旋涂方式形成，能够得到更平整、更均匀、效率更高、更加稳定的薄膜。相较于常用的一步退火以及有毒反溶剂的方法，梯度退火的方法能形成更加致密的薄膜以及更纯的相态；绿色反溶剂的使用摒弃了传统的有毒反溶剂，有效减少了环境污染。并且，在微观结构上，反溶剂处理的薄膜晶粒达到微米级别，晶界极少，整个薄膜的缺陷态也因此得到了抑制，这也为钙钛矿薄膜的热稳定性和湿度稳定性提供了保障。

Description

基于梯度退火与反溶剂协同效应制备无机钙钛矿电池的方法及制备的无机钙钛矿电池 技术领域
本发明涉及一种太阳能电池，具体涉及一种全无机钙钛矿太阳能电池及其制备方法，尤其涉及基于梯度退火与反溶剂协同效应制备无机钙钛矿电池的方法及制备的无机钙钛矿电池。
背景技术
无机钙钛矿太阳能电池采用叠层结构，将无机钙钛矿活性层置于电子传输层和空穴传输层之间，避免了钙钛矿与阳极和阴极的直接接触而降低太阳能的转换效率，一般采用有机小分子或聚合物作为空穴传输层的材料，采用金属氧化物作为电子传输层的材料。钙钛矿活性层的成膜质量对于太阳能电池的光电转换效率起着至关重要的作用，目前制备无机钙钛矿的主要方法为溶液成膜法，溶液成膜法一般需要反溶剂加速晶体析出，从而加快晶体的生长；而现有使用的反溶剂通常为氯苯、氯仿等有毒溶剂，并不是绿色溶剂，会对环境产生很大的影响；另外，无机钙钛矿薄膜中的小晶粒以及多孔的形貌会降低电池的整体性能。
技术问题
本发明的目的在于提供一种全无机钙钛矿太阳能电池及其制备方法，利用梯度退火以及绿色反溶剂的方法有效提高太阳能电池的光电转化效率，整个电池制备过程不需要高温煅烧，重复性高，操作方便。
技术解决方案
本发明采用如下技术方案：
一种基于梯度退火与反溶剂协同效应制备无机钙钛矿电池的方法，采用梯度退火和反溶剂处理的方法制备钙钛矿层。
本发明中，所述钙钛矿层的厚度为100～1000nm；制备钙钛矿层的钙钛矿前驱体溶液中，溶剂为酰胺类溶剂和/或砜类溶剂，优选DMF和/或DMSO，更优选DMSO；制备钙钛矿层的钙钛矿前驱体溶液 的浓度为0.4～2M，优选1～1.8M；所述梯度退火的工艺为40～70℃/0.5～5min+70～130℃/0.5～5min+130～160℃/5～20min+160～280℃/0～20mi，优选的，所述梯度退火的工艺为40～60℃/1～2min+80～120℃/1～2min+150～180℃/5～15min+180～200℃/0～2min；所述反溶剂为醇类溶剂、苯类溶剂或者醚类溶剂；制备钙钛矿层时，旋涂转速为2500～3500rpm，时间为25～45秒。现有技术为了获得较高质量的薄膜，一般采用较低浓度的前驱体溶液(小于0.8M)，以及含有大量DMF的混合溶剂，但是为了得到接近300nm的膜厚，现有方法一般伴随着较低的转速，小于1500rpm，从而在成膜质量方面得不到保证；本发明采用纯DMSO作为溶剂从而保证了高浓度前驱体溶液，经过高速旋涂(3000rpm)，在取得高质量薄膜(表面平整均匀、稳定性好、重复性好，缺陷较少)的同时，膜厚能达到500nm，取得了意想不到的技术效果。
本发明中，所述钙钛矿为全无机CsPb xSn 1-xI yBr 3-y，其中0≤y≤3，0≤x≤1；或者Cs aK bRb 1-a-bPb cSn dCa eMg 1-c-d-eI yBr 3-y，其中0≤a≤1，0≤b≤1，0≤c≤1，0≤d≤1，0≤e≤1，a+b＝1，c+d+e＝1，0≤y≤3；或者CuInGaSn、CsAgBiI(Br)、Cs xFA yMA 1-x-yPbI zBr 3-z，其中0≤x≤1，0≤y≤1，x+y≤1，0≤z≤3。
本发明首次采用梯度退火以及绿色反溶剂的方法在电子(空穴)传输层上制备无机钙钛矿层，制备的无机钙钛矿活性层膜表面平整均匀、晶粒较大、晶界较少、稳定性好、重复性好，无需有毒溶剂；尤其是本发明制备的无机钙钛矿具有极强的结晶强度，使得钙钛矿分子取向极高，薄膜质量高，制备成完整器件以后表现出极高的光电转化效率。
本发明所述基于梯度退火与反溶剂协同效应制备无机钙钛矿电池的方法，具体包括以下步骤：
(1)在透明基底上制备阴极；
(2)在阴极上制备电子传输层；
(3)采用梯度退火和反溶剂处理的方法在电子传输层上制备钙钛矿层；
(4)在钙钛矿层上制备空穴传输层；
(5)在空穴传输层上制备电极，得到钙钛矿太阳能电池；
以上得到n-i-p型电池；
或者
(1)在透明基底上制备阳极；
(2)在阳极上制备空穴传输层；
(3)采用梯度退火和反溶剂处理的方法在空穴传输层上制备钙钛矿层；
(4)在钙钛矿层上制备电子传输层；
(5)在电子传输层上制备电极，得到钙钛矿太阳能电池；
以上得到p-i-n型电池。
一种无机钙钛矿电池用钙钛矿薄膜的制备方法，包括以下步骤：
(1)在透明基底上制备阴极；
(2)在阴极上制备电子传输层；
(3)采用梯度退火和反溶剂处理的方法在电子传输层上制备钙钛矿薄膜；
或者
(1)在透明基底上制备阳极；
(2)在阳极上制备空穴传输层；
(3)采用梯度退火和反溶剂处理的方法在空穴传输层上制备钙钛矿薄膜。
本发明利用梯度退火以及绿色反溶剂法制备的无机钙钛矿薄膜在成膜均一性、平整性方面有了很大的改观，器件的效率以及稳定性也得到了进一步的提高。宽带隙的无机钙钛矿电池(吸收边680nm)在保证较高的光电转化效率的同时，也为半透明电池以及叠层电池的发展提供了重要的帮助。
本发明中，所述透明基底为玻璃基底、石英基底、PET塑料基底、PEN塑料基底、柔性网格银基底中的一种；所述阴极为氧化铟锡或者氟掺杂二氧化锡；所述阳极为氧化铟锡或者氟掺杂二氧化锡；采用磁控溅射的方法在透明基底上制备阴极或者阳极；所述电子传输层 材料为ZnO、TiO 2、SnO 2、PCBM、富勒烯、富勒烯衍生物中的一种或几种；所述空穴传输层材料选自聚[双(4-苯基)(2,4,6-三甲基苯基)胺]、聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸盐、氧化镍、氧化铜、2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴、硫氰酸亚铜、氧化钼中的一种。
本发明可以选用镀上一层氧化铟锡薄膜的导电玻璃，俗称ITO，作为电池的阴极/阳极；还可以用掺杂氟的SnO 2导电玻璃，俗称FTO，作为阴极/阳极。
上述技术方案中，步骤(2)中，在n-i-p型结构中所述电子传输层为ZnO、TiO 2、SnO 2等金属氧化物或金属氧化的复合传输层、PCBM、C 60等富勒烯及富勒烯衍生物以及有机无机杂化的电子传输层中的一种或几种；采用旋涂后退火的方法在阴极上制备电子传输层，所述旋涂的速度为1000～5000rpm，时间为10～60s，厚度为10～100nm，退火的温度为100～300℃，时间为10～60min。p-i-n型结构所述空穴传输层选自聚[双(4-苯基)(2,4,6-三甲基苯基)胺]等具有三苯胺结构的聚合物，聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸盐等p型半导体与有机盐的结合体，氧化镍、氧化铜等金属氧化物中的一种；采用旋涂的方法在钙钛矿层上制备空穴传输层，所述旋涂的速度为1000～6000rpm，时间为20～60s，厚度为5～200nm；p-i-n型结构所述空穴传输层选自聚[双(4-苯基)(2,4,6-三甲基苯基)胺]等具有三苯胺结构的聚合物，聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸盐等p型半导体与有机盐的结合体，氧化镍、氧化铜等金属氧化物中的一种；采用旋涂的方法在阳极上制备空穴传输层，所述旋涂的速度为1000～6000rpm，时间为20～60s，厚度为5～200nm。
上述技术方案中，步骤(4)中，n-i-p型结构所述空穴传输层选自2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴类小分子、聚[双(4-苯基)(2,4,6-三甲基苯基)胺]等三苯胺结构化合物、硫氰酸亚铜、氧化镍、氧化铜、氧化钼等金属氧化物中的一种；采用旋涂的方法在钙钛矿层上制备空穴传输层，所述旋涂的速度为1000～6000rpm，时间为20～60s，厚度为50～300nm。在p-i-n型结构中所述的电子传输层 包括ZnO等金属氧化物，PCBM等富勒烯和富勒烯衍生物，无机氧化物与有机物的复合电子传输层。采用旋涂后退火的方法在阳极上制备电子传输层，所述旋涂的速度为1000～5000rpm，时间为10～60s，厚度为10～100nm，退火的温度为100～300℃，时间为10～60min。在p-i-n型结构中所述的电子传输层包括ZnO等金属氧化物，PCBM等富勒烯和富勒烯衍生物，无机氧化物与有机物的复合电子传输层。采用旋涂后退火的方法在钙钛矿层上制备电子传输层，所述旋涂的速度为1000～5000rpm，时间为10～60s，厚度为10～100nm，退火的温度为100～300℃，时间为10～60min。
本发明中，所述电极为Au电极、Ag电极、Al电极、Cu电极、碳电极、PH1000聚合物电极、金属氧化物电极中的一种或几种。
上述技术方案中，步骤(5)中，采用蒸镀或者转移的方法在空穴(或者电子)传输层上制备电极；所述电极的厚度为10～200nm；所述电极为Au电极、Ag电极、Al电极、Cu电极等高导电金属或复合金属电极、碳电极、PH1000等聚合物电极、金属氧化物电极中的一种。
根据上述制备方法制备的无机钙钛矿电池或者无机钙钛矿电池用钙钛矿薄膜。
上述无机钙钛矿电池用钙钛矿薄膜在制备无机钙钛矿电池中的应用。
本发明的钙钛矿太阳能电池具备效率高、成本低、方便制备的优点，同时由于钙钛矿材料具有较好的光吸收、较长的载流子传输距离、较弱的激子结合能以及极少的表面缺陷态等特点使其成为一种极具竞争力材料，在电池和发光领域应用前景广泛。
本发明公开的全无机的钙钛矿薄膜相较于传统的有机无机杂化钙钛矿薄膜，在热稳定性方面有了质的提高，无机钙钛矿薄膜在300℃左右也不会发生分解，解决了有机无机杂化钙钛矿薄膜成分热分解的本质问题；高质量的无机薄膜加上较宽的带隙(吸收边680nm)使得整个电池在保证高光电转化效率的同时，为半透明电池以及叠层电池的发展提供了重要的帮助，与有机太阳能电池、钙钛矿电池、硅电池、CIGS电池相结合，能够有效提高叠层电池的效率；此外，高质量 的钙钛矿薄膜在LED领域应用前景广阔，在添加正向电压的情况下，由于薄膜较少的缺陷态，单分子复合能够被有效抑制，从而使注入的电子和空穴更易发生辐射复合，提高红光的发光效率。
有益效果
1.本发明选择利用梯度退火以及反溶剂的方式制备钙钛矿层，得到的钙钛矿层薄膜表面平整均匀、稳定性好、重复性好，缺陷较少，光电转化效率高；并且高质量的无机钙钛矿薄膜在LED领域也有很好的应用前景；
2.本发明利用绿色反溶剂，摒弃了传统有毒反溶剂，有效减少了环境污染；
3.本发明制备的宽带隙无机钙钛矿太阳能电池带隙较宽，对680nm之前的光有极高的利用率，并且其较窄的吸收有望作为叠层电池的底电池，提高叠层电池的光电转化效率；
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。本发明的具体实施方式由以下实施例及其附图详细给出。
附图说明
图1为实施例一CsPbI 2Br直接高温退火和梯度退火的照片；
图2为实施例一CsPbI 2Br直接高温退火和梯度退火的SEM图；
图3为实施例一CsPbI 2Br钙钛矿层SEM截面图，由下而上依次为Glass/ITO/TiO 2/CsPbI 2Br/Spiro-OMeTAD/Au；
图4为实施例一CsPbI 2Br钙钛矿电池直接高温退火和梯度退火的J-V曲线图；
图5为实施例二CsPbI 2Br钙钛矿薄膜在异丙醇处理以后直接高温退火的SEM图；
图6为实施例二CsPbI 2Br钙钛矿层在不同反溶剂处理后梯度退火颜色变化图；
图7为实施例二不同反溶剂处理的CsPbI 2Br薄膜在50℃退火1分钟以后的SEM图；
图8为实施例二空白CsPbI 2Br钙钛矿薄膜边缘条纹处与中心处光学显微镜图像以及SEM图像的对比；
图9为实施例二异丙醇处理的CsPbI 2Br薄膜镜面反射的照片；
图10为实施例二不同反溶剂处理的CsPbI 2Br薄膜的SEM图；
图11为实施例二不同反溶剂处理的CsPbI 2Br器件J-V曲线图；
图12为实施例二梯度退火以及反溶剂协同作用的模拟图；
图13为实施例二梯度退火与反溶剂协同作用下，CsPbI 2Br器件的湿度稳定性。
本发明的实施方式
下面将结合实施例，详细说明本发明：
实施例一
(1)采用玻璃的刚性基底，进行抛光，然后在玻璃上用磁控溅射的方法镀上一层氧化铟锡薄膜，形成ITO导电玻璃，作为太阳能电池的阴极；
(2)在ITO导电玻璃上旋涂TiO 2溶液，3000rpm30s，然后150℃退火30min，得到厚度为20nm的电子传输层；
(3)将旋涂有电子传输层的ITO置于氮气手套箱中旋涂钙钛矿前驱体溶液，溶液的组分为PbI 2、CsI和PbBr 2，组成浓度为1.3M的CsPbI 2Br溶液；溶剂为纯DMSO；前驱体溶液搅拌两小时以后过滤即可使用；旋涂的速率为3000rpm，时间为30s，旋涂完毕后进行梯度退火，先在50℃下退火1分钟，然后在100℃下退火1分钟，最后在160℃下退火10分钟得到无机钙钛矿薄膜，并以一步退火为对比；附图1为直接一步高温退火(160℃/10min或者100℃/12min)和进行梯度退火(50℃/1min+100℃/1min+160℃/10min)的无机钙钛矿薄膜的照片，由图可知，直接高温退火的薄膜表面非常粗糙，而梯度退火的薄膜表面较为光滑说明了梯度退火对于改善薄膜质量的重要性；
图2为直接一步高温退火和进行梯度退火的无机钙钛矿薄膜的扫描电子显微镜图(SEM)，由图可知，直接高温退火的薄膜覆盖率较低，而梯度退火的薄膜覆盖率很高，成膜性较好；
(4)将得到的钙钛矿薄膜置于真空吸盘上，旋涂Spiro-OMeTAD (2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴)作为空穴传输层，转速3000rpm，时间30s，然后在干燥的空气中氧化12h，得到厚度为150nm的空穴传输层；
(5)将氧化后的空穴传输层置于镀膜机中蒸镀Au电极，厚度为80nm。
至此，CsPbI 2Br的钙钛矿电池制备完成，结构见图3，空白表示未经反溶剂处理，甲苯、异丙醇表示分别经过甲苯、异丙醇反溶剂处理，可以看出，钙钛矿膜厚500nm。
图4和表1是CsPbI 2Br的钙钛矿电池直接高温退火(160℃/10min)以及梯度退火的效率表以及J-V曲线图。由此可知，直接高温退火的薄膜成膜性极差，因此电池的各项性能参数都不佳，这主要归因于钙钛矿较差的薄膜覆盖率导致的上下传输层直接接触。而经过梯度退火的钙钛矿电池性能较为优异，与已报道的无机钙钛矿电池的最高效率相当；100℃直接高温退火后的电池PCE为3.49％。
表1 直接高温退火和梯度退火法制得的无机钙钛矿电池性能
Figure PCTCN2018099716-appb-000001
实施例二
(1)采用玻璃的刚性基底，进行抛光，然后在玻璃上用磁控溅射的方法镀上一层氧化铟锡薄膜，形成ITO导电玻璃，作为太阳能电池的阴极；
(2)在ITO导电玻璃上旋涂TiO 2溶液，3000rpm30s，然后150℃退火30min，得到厚度为20nm的电子传输层；
(3)将旋涂有电子传输层的ITO置于氮气手套箱中旋涂钙钛矿前驱体溶液，溶液的组分为PbI 2,CsI和PbBr 2，组成浓度为1.3M的CsPbI 2Br溶液；溶剂为纯DMSO；前驱体溶液搅拌两小时以后过滤即可使用。旋涂的速率为3000rpm，时间为30s，在旋涂20s时滴加150微升异丙醇或者甲苯溶液，旋涂完毕后进行梯度退火，薄膜先在50℃下退火1分钟，然后在100℃下退火1分钟，最后在160℃下退火10分钟得到无机钙钛矿薄膜；值得一提的是，如果没有梯度退火的过程，滴加完 反溶剂以后直接100℃或者更高的温度退火，得到的SEM图见图5，晶粒不能完整的覆盖整个薄膜，孔隙较大，这与不添加反溶剂直接高温退火的SEM形貌类似，制备电池的PCE为5.73％，如果选用80℃/1min+120℃/8min，得到电池的PCE为6.83％；这更加证明了本发明梯度退火对于薄膜质量的重要性。
对不同反溶剂处理的薄膜进行原位表征，如图6，在梯度退火的第一阶段50℃退火时，相较于不用反溶剂处理的薄膜(空白)，用甲苯或者异丙醇(IPA)处理的薄膜在结晶时更加均匀；SEM图也显示反溶剂处理的薄膜在第一阶段的退火以后拥有更平整的薄膜以及更大的晶粒(图7)；整个梯度退火完成以后，不用反溶剂处理的薄膜在边缘有较多的条纹，这主要是由于薄膜退火不均匀所导致的，并且这些条纹处的光学显微镜图与SEM图显示有较多的孔洞(图8)，这对于器件性能的影响很大；相比空白薄膜的中心处，光学显微镜图与SEM图则显示出较为致密的薄膜；而利用甲苯或者异丙醇处理的薄膜，在第一步退火时较为均匀(尤其异丙醇)，最后得到的薄膜表面粗糙度更小，并且整个薄膜非常均匀，边缘没有白色不均一的条纹，这为高性能的器件提供了保障。
图9是异丙醇处理的薄膜镜面反射的图片，充分说明了薄膜的均一性与平整性；图10是不同反溶剂处理的薄膜SEM图，从图中可知，异丙醇处理的薄膜拥有微米级大小的晶粒，远远优于无反溶剂处理或者甲苯处理的钙钛矿薄膜，这也是异丙醇处理的器件性能优异的原因，相关的器件参数以及J-V曲线见表2和图11，梯度退火以及反溶剂协同作用的模拟图见图12。说明本发明可以采用高浓度的前驱体溶液，采用高转速，获得高厚度、高质量的钙钛矿薄膜，克服了现有技术低浓度、低转速才能获得较高厚度薄膜的技术缺陷，解决了现有钙钛矿薄膜孔洞较多、晶粒较小等技术缺陷；取得了意想不到的技术效果。
(4)将钙钛矿薄膜置于真空吸盘上，旋涂Spiro-OMeTAD空穴传输层，转速3000rpm30s，在干燥的空气中氧化12h，得到厚度为150nm的空穴传输层；
(5)将氧化后的空穴传输层置于镀膜机中蒸镀Au电极，厚度为80nm，至此，CsPbI 2Br的钙钛矿电池制备完成。不同反溶剂处理的器件结构见图3，由图可知，三种条件下钙钛矿薄膜的厚度都达到了500nm，并且异丙醇处理的器件薄膜晶界更少，有利于性能的提高。
不同反溶剂处理的薄膜晶体质量不一致，从而导致器件的稳定性也有所差异，如图13。在25℃，30％的湿度下贮存1000个小时，IPA处理的器件能维持初始效率的95％，甲苯处理的器件能维持初始效率的70％，而空白的器件效率衰减到初始效率的56％。由此可见，晶体质量对器件的稳定性影响很大，较大的晶粒伴随较少的缺陷态有助于抑制薄膜自身的降解，从而使器件性能保持稳定。本发明中，钙钛矿薄膜的制备过程中，前驱体溶液的浓度以及成分可以做调整，这里就不做赘述。
表2 不同反溶剂处理的器件性能
Figure PCTCN2018099716-appb-000002
本发明采用梯度退火以及绿色反溶剂处理无机钙钛矿薄膜，得到晶粒较大，纯度较高，稳定性较好的薄膜。利用这种方法制备的无机钙钛矿薄膜热稳定性较好，在高温下不降解，并且在较低的湿度下具有很好的稳定性；并且，这种方法制备的无机钙钛矿电池效率突破了16％，是无机钙钛矿领域的最高效率。

Claims (10)

  1. 一种基于梯度退火与反溶剂协同效应制备无机钙钛矿电池的方法，其特征在于，采用梯度退火和反溶剂处理的方法制备钙钛矿层。
  2. 根据权利要求1所述基于梯度退火与反溶剂协同效应制备无机钙钛矿电池的方法，其特征在于，所述钙钛矿层的厚度为100～1000nm；制备钙钛矿层的钙钛矿前驱体溶液中，溶剂为酰胺类溶剂和/或砜类溶剂；制备钙钛矿层的钙钛矿前驱体溶液的浓度为0.4～2M；所述梯度退火的工艺为40～70℃/0.5～5min+70～130℃/0.5～5min+130～160℃/5～20min+160～280℃/0～20min；所述反溶剂为醇类溶剂、苯类溶剂或者醚类溶剂。
  3. 根据权利要求1所述基于梯度退火与反溶剂协同效应制备无机钙钛矿电池的方法，其特征在于，所述钙钛矿为全无机CsPb xSn 1-xI yBr 3-y，其中0≤y≤3，0≤x≤1；或者Cs aK bRb 1-a-bPb cSn dCa eMg 1-c-d-eI yBr 3-y，其中0≤a≤1，0≤b≤1，0≤c≤1，0≤d≤1，0≤e≤1，a+b＝1，c+d+e＝1，0≤y≤3；或者CuInGaSn、CsAgBiI(Br)、Cs xFA yMA 1-x-yPbI zBr 3-z，其中0≤x≤1，0≤y≤1，x+y≤1，0≤z≤3。
  4. 根据权利要求1所述基于梯度退火与反溶剂协同效应制备无机钙钛矿电池的方法，其特征在于，包括以下步骤：
    (1)在透明基底上制备阴极；
    (2)在阴极上制备电子传输层；
    (3)采用梯度退火和反溶剂处理的方法在电子传输层上制备钙钛矿层；
    (4)在钙钛矿层上制备空穴传输层；
    (5)在空穴传输层上制备电极，得到钙钛矿太阳能电池；
    或者
    (1)在透明基底上制备阳极；
    (2)在阳极上制备空穴传输层；
    (3)采用梯度退火和反溶剂处理的方法在空穴传输层上制备钙钛矿层；
    (4)在钙钛矿层上制备电子传输层；
    (5)在电子传输层上制备电极，得到钙钛矿太阳能电池。
  5. 一种无机钙钛矿电池用钙钛矿薄膜的制备方法，其特征在于，包括以下步骤：
    (1)在透明基底上制备阴极；
    (2)在阴极上制备电子传输层；
    (3)采用梯度退火和反溶剂处理的方法在电子传输层上制备钙钛矿薄膜；
    或者
    (1)在透明基底上制备阳极；
    (2)在阳极上制备空穴传输层；
    (3)采用梯度退火和反溶剂处理的方法在空穴传输层上制备钙钛矿薄膜。
  6. 根据权利要求4或者5所述的制备方法，其特征在于，所述透明基底为玻璃基底、石英基底、PET塑料基底、PEN塑料基底、柔性网格银基底中的一种；所述阴极为氧化铟锡或者氟掺杂二氧化锡；所述阳极为氧化铟锡或者氟掺杂二氧化锡；所述电子传输层材料为ZnO、TiO 2、SnO 2、PCBM、富勒烯、富勒烯衍生物中的一种或几种；所述空穴传输层材料选自聚[双(4-苯基)(2,4,6-三甲基苯基)胺]、聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸盐、氧化镍、氧化铜、2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴、硫氰酸亚铜、氧化钼中的一种。
  7. 根据权利要求4所述的制备方法，其特征在于，所述电极为Au电极、Ag电极、Al电极、Cu电极、碳电极、PH1000聚合物电极、金属氧化物电极中的一种或几种。
  8. 根据权利要求1所述的制备方法制备的无机钙钛矿电池。
  9. 根据权利要求5所述的制备方法制备的无机钙钛矿电池用钙钛矿薄膜。
  10. 权利要求9所述无机钙钛矿电池用钙钛矿薄膜在制备权利要求8所述无机钙钛矿电池中的应用。
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