WO2020206872A1 - 梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜及其制备方法 - Google Patents

梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜及其制备方法 Download PDF

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WO2020206872A1
WO2020206872A1 PCT/CN2019/098047 CN2019098047W WO2020206872A1 WO 2020206872 A1 WO2020206872 A1 WO 2020206872A1 CN 2019098047 W CN2019098047 W CN 2019098047W WO 2020206872 A1 WO2020206872 A1 WO 2020206872A1
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film
hybrid perovskite
precursor solution
gradient structure
spacer
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吴刚
连小梅
陈杰焕
陈红征
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Zhejiang University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • 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
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    • 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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  • the invention belongs to the field of organic-inorganic hybrid perovskite materials, and specifically relates to a two-dimensional Ruddlesden-Popper hybrid perovskite film with gradient structure characteristics and a preparation method thereof.
  • spacer cations will form an insulating layer in the two-dimensional perovskite and hinder the transport of carriers. Moreover, the presence of spacer cations will also limit the growth of crystal grains, leading to an increase in grain boundaries in the two-dimensional perovskite film, resulting in serious carrier recombination, and thereby degrading the performance of the optoelectronic device.
  • the method to avoid the hindrance of carrier transmission by the spacer cation insulating layer is mainly to make the crystals in the two-dimensional perovskite film grow perpendicular to the substrate orientation, and the method to achieve this is mainly high temperature (>100°C) thermal spin coating , Use mixed solvents (such as DMF and DMSO mixed) and add volatile additives (such as ammonium thiocyanate) and so on.
  • the distribution of spacer cations all show the characteristics of decreasing upward in the thickness direction.
  • the two-dimensional hybrid perovskite film with high charge transport ability and high moisture resistance needs to have the following characteristics: 1.
  • the film is composed of large grains that grow perpendicular to the substrate; 2.
  • Spacer cations are enriched on the upper surface, and the concentration distribution decreases downward along the thickness of the film.
  • the purpose of the present invention is to solve the above-mentioned problems in the prior art and provide a two-dimensional Ruddlesden-Popper hybrid perovskite film with a gradient structure.
  • the film is composed of oriented large crystal grains, has good carrier transport characteristics, and has a gradient structure feature in which one of the spacer cations is enriched on the surface of the film, which is beneficial to obtain good moisture resistance stability.
  • a two-dimensional Ruddlesden-Popper hybrid perovskite film with gradient structure which is obtained by deposition of a precursor solution containing two spacer cations, one of which is n-butylammonium, and the second Species are phenethylammonium, benzalkonium, tert-butylammonium, imidazolium, ethylpyridinium or isobutylammonium; and the second spacer cation is enriched on the surface of the film, forming a concentration gradient that decreases downward along the thickness of the film .
  • n-butylammonium, phenethylammonium, benzalkonium, tert-butylammonium, imidazolium, ethylpyridinium or isobutylammonium mentioned herein in the present invention all refer to the cation of the corresponding compound.
  • the present invention can further provide one or more of the following preferred implementation modes. It should be pointed out that the technical features of each preferred implementation manner of the present invention can be combined accordingly without conflicts.
  • the molar ratio of n-butylammonium to the second spacer cation is 1:0.01-0.3.
  • the precursor solution is a mixture of methylamine hydroiodide, two spacer cation hydroiodides, lead iodide and an organic solvent, and the organic solvent is formamide, dimethyl sulfoxide, One or a mixture of N,N-dimethylformamide.
  • the ratio of lead iodide to organic solvent in the precursor solution is 50-800 mg: 1 ml.
  • methylamine hydroiodide lead iodide are 2:2:3 or 2:3:4 or 2: 4:5.
  • the specific process of the deposition is: spin-coating the precursor solution on the substrate to form a film, and annealing.
  • the temperature of the substrate is 25-70°C, and the temperature of the precursor solution is the same as that of the substrate.
  • the annealing temperature range is 70-150°C, and the annealing time range is 5-20 minutes.
  • the substrate is an ITO glass substrate spin-coated with a PEDOT:PSS layer.
  • Another object of the present invention is to provide a method for preparing a two-dimensional Ruddlesden-Popper hybrid perovskite film with gradient structure characteristics. The steps are as follows:
  • the two spacer cations hydroiodide, methylamine hydroiodide, lead iodide and an organic solvent are mixed to obtain a precursor solution; in the precursor solution, one of the two spacer cations is n-butylammonium,
  • the second type is phenethylammonium, benzalkonium, tert-butylammonium or isobutylammonium, the molar ratio of n-butylammonium to the second spacer cation is 1:0.01 ⁇ 0.3, and the ratio of lead iodide to organic solvent is 50 -800 mg: 1 ml, the organic solvent is a mixture of one or more of formamide, dimethyl sulfoxide, and N,N-dimethylformamide, in terms of molar ratio, two kinds of intervening cation hydrogen Iodate: methylamine hydroiodide: lead iodide is 2:2:3 or 2:3:4 or 2:4:5;
  • the precursor solution is spin-coated on the substrate to form a film, and then annealed; during spin-coating, the temperature of the substrate is 25-70°C, the temperature of the precursor solution used for spin-coating is the same as that of the substrate, and the annealing temperature range is 70 -150°C, annealing time range is 5-20 minutes.
  • the present invention adopts a perovskite precursor solution containing two spacer cations.
  • a two-dimensional hybrid Ruddlesden-Popper hybrid perovskite film composed of oriented large crystal grains is obtained, thereby obtaining a good load.
  • Current transport capacity; on the other hand, one of the two spacer cations can be enriched on the surface of the film to form a concentration gradient that decreases downward in the thickness direction, which is conducive to obtaining good moisture resistance stability. It is of great significance for the solution preparation of high-performance hybrid perovskite optoelectronic devices.
  • Figure 1 is a cross-sectional SEM image of a two-dimensional Ruddlesden-Popper hybrid perovskite film with a gradient structure.
  • Figure 2 is the time-of-flight secondary ion mass spectrometry (TOF-SIMS) data of the distribution of phenethylammonium cations in the film.
  • the left side is the upper surface of the film, and the right side is the lower surface of the film.
  • Figure 3 shows the changes in the X-ray diffraction (XRD) pattern of the two-dimensional Ruddlesden-Popper hybrid perovskite film stored in the air with a humidity of 50 ⁇ 5% with storage time (0 days to 120 days).
  • XRD X-ray diffraction
  • the preparation process of the two-dimensional Ruddlesden-Popper hybrid perovskite film with gradient structure is as follows: first, the ITO glass substrate is washed with detergent, acetone, isopropanol, and ethanol for 5 minutes, then rinsed with deionized water. drying. After UV-ozone treatment, a PEDOT:PSS layer with a thickness of about 25 nm was prepared by a spin coating method, and baked at 140°C for 15 minutes and then taken out. Mix two spacer cations hydroiodide, methylamine hydroiodide, and lead iodide with organic solvents.
  • One of the two spacer cations is n-butylammonium, and the second is phenethylammonium, benzylammonium, and tert-butyl.
  • Ammonium or isobutyl ammonium the molar ratio of n-butyl ammonium to the second spacer cation is 1:0.01 ⁇ 0.3; the ratio of lead iodide to organic solvent is 50-800 mg: 1 ml; the organic solvent is formamide, two Methyl sulfoxide, N,N-dimethylformamide and their mixtures; spacer cation hydroiodide: methylamine hydroiodide: lead iodide ratio (molar ratio) is 2:2:3 or 2: 3:4 or 2:4:5.
  • the precursor solution is spin-coated on the substrate to form a film, and then annealed.
  • the temperature of the substrate is 25-70°C, and the temperature of the spin coating precursor solution is the same as the temperature of the substrate.
  • the annealing temperature range is 70-150°C, and the annealing time range is 5-20 minutes.
  • the ITO glass substrate was ultrasonically washed with detergent, acetone, isopropanol, and ethanol for 5 minutes, then rinsed with deionized water and dried. After the dried ITO glass substrate is treated with ultraviolet-ozone, a PEDOT:PSS layer with a thickness of about 25 nm is prepared by a spin coating method, and it is baked at 140°C for 15 minutes and then taken out. Mix and dissolve phenethylamine hydroiodide, n-butylamine hydroiodide, methylamine hydroiodide, and lead iodide in N,N-dimethylformamide.
  • FIG. 1 The scanning electron microscope (SEM) photograph of the cross-section of the film is shown in Figure 1, which shows that the film is composed of large crystal grains oriented along the thickness direction.
  • Figure 2 Time-of-flight secondary ion mass spectrometry (TOF-SIMS) data shows that the concentration distributions of two spacer cations in the perovskite film are different. Among them, the phenethylammonium cation PEA + is enriched on the surface, that is, the PEA + concentration on the film surface is the largest. And form a concentration gradient that decreases downward along the thickness direction.
  • the stability test of Fig. 3 shows that the X-ray diffraction (XRD) pattern of the film is almost unchanged when the film is stored in the air with a humidity of 50 ⁇ 5% for 120 days, showing good humidity resistance stability.
  • XRD X-ray diffraction
  • the ITO glass substrate was ultrasonically washed with detergent, acetone, isopropanol, and ethanol for 5 minutes, then rinsed with deionized water and dried. After the dried ITO glass substrate is treated with ultraviolet-ozone, a PEDOT:PSS layer with a thickness of about 25 nm is prepared by a spin coating method, and it is baked at 140°C for 15 minutes and then taken out. Mix and dissolve benzylamine hydroiodide, n-butylamine hydroiodide, methylamine hydroiodide, and lead iodide in formamide. The ratio of lead iodide to formamide is 800 mg: 1 ml.
  • N-butylamine hydroiodide+benzylamine hydroiodide methylamine hydroiodide: lead iodide (molar ratio) is 2:4:5, n-butylammonium: benzylammonium (in ion mole The ratio) is 1:0.3, stirred overnight to obtain the precursor solution; using the solution spin coating method, take the 30°C precursor solution and spin-coat the 30°C PEDOT:PSS on the ITO glass substrate to form a film, and then 150°C annealing 20 Minutes, a high-quality two-dimensional Ruddlesden-Popper hybrid perovskite film with a gradient structure was obtained.
  • the ITO glass substrate was ultrasonically washed with detergent, acetone, isopropanol, and ethanol for 5 minutes, then rinsed with deionized water and dried. After the dried ITO glass substrate is treated with ultraviolet-ozone, a PEDOT:PSS layer with a thickness of about 25 nm is prepared by a spin coating method, and it is baked at 140°C for 15 minutes and then taken out. Dissolve tert-butylamine hydroiodide, n-butylamine hydroiodide, methylamine hydroiodide, and lead iodide in dimethyl sulfoxide.
  • the ratio of lead iodide to dimethyl sulfoxide is 400 mg :1ml, (n-butylamine hydroiodide + tert-butylamine hydroiodide): methylamine hydroiodide: lead iodide (molar ratio) is 2:3:4, n-butylammonium: tert-butylammonium (in Ion molar ratio) is 1:0.2, stirred overnight to obtain the precursor solution; using the solution spin coating method, take the 70°C precursor solution and spin-coated the 70°C PEDOT:PSS on the ITO glass substrate, 100°C Annealed for 15 minutes to obtain a high-quality two-dimensional Ruddlesden-Popper hybrid perovskite film with a gradient structure.
  • the scanning electron microscope (SEM) photograph obtained is similar to Figure 1
  • the time-of-flight secondary ion mass spectrometry (TOF-SIMS) obtained is similar to Figure 2.
  • Figure 1 and Figure 2 show that a high-quality two-dimensional Ruddlesden-Popper hybrid perovskite film with a gradient structure is formed.
  • the stability of the film when stored in the air with a humidity of 50 ⁇ 5% for 120 days was investigated.
  • the X-ray diffraction (XRD) pattern of the film was similar to that in Figure 3, indicating its good moisture resistance stability.
  • the ITO glass substrate was ultrasonically washed with detergent, acetone, isopropanol, and ethanol for 5 minutes, then rinsed with deionized water and dried. After the dried ITO glass substrate is treated with ultraviolet-ozone, a PEDOT:PSS layer with a thickness of about 25 nm is prepared by a spin coating method, and it is baked at 140°C for 15 minutes and then taken out.
  • the ITO glass substrate was ultrasonically washed with detergent, acetone, isopropanol, and ethanol for 5 minutes, then rinsed with deionized water and dried. After the dried ITO glass substrate is treated with ultraviolet-ozone, a PEDOT:PSS layer with a thickness of about 25 nm is prepared by a spin coating method, and it is baked at 140°C for 15 minutes and then taken out. Dissolve imidazole hydroiodide, n-butylamine hydroiodide, methylamine hydroiodide, and lead iodide in N,N-dimethylformamide/formamide.
  • the ITO glass substrate was ultrasonically washed with detergent, acetone, isopropanol, and ethanol for 5 minutes, then rinsed with deionized water and dried. After the dried ITO glass substrate is treated with ultraviolet-ozone, a PEDOT:PSS layer with a thickness of about 25 nm is prepared by a spin coating method, and it is baked at 140°C for 15 minutes and then taken out.
  • the ITO glass substrate was ultrasonically washed with detergent, acetone, isopropanol, and ethanol for 5 minutes, then rinsed with deionized water and dried. After the dried ITO glass substrate is treated with ultraviolet-ozone, a PEDOT:PSS layer with a thickness of about 25 nm is prepared by a spin coating method, and it is baked at 140°C for 15 minutes and then taken out.
  • the scanning electron microscope (SEM) photograph obtained is similar to Figure 1
  • the time-of-flight secondary ion mass spectrometry (TOF-SIMS) obtained is similar to Figure 2.
  • Figure 1 and Figure 2 show that a high-quality two-dimensional Ruddlesden-Popper hybrid perovskite film with a gradient structure is formed.
  • the stability of the film when stored in the air with a humidity of 50 ⁇ 5% for 120 days was investigated.
  • the X-ray diffraction (XRD) pattern of the film was similar to that in Figure 3, indicating its good moisture resistance stability.
  • the ITO glass substrate was ultrasonically washed with detergent, acetone, isopropanol, and ethanol for 5 minutes, then rinsed with deionized water and dried. After the dried ITO glass substrate is treated with ultraviolet-ozone, a PEDOT:PSS layer with a thickness of about 25 nm is prepared by a spin coating method, and it is baked at 140°C for 15 minutes and then taken out. Mix and dissolve phenethylamine hydroiodide, n-butylamine hydroiodide, methylamine hydroiodide, and lead iodide in N,N-dimethylformamide.

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Abstract

涉及一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜及其制备方法，属于有机-无机杂化钙钛矿材料领域。该薄膜可以通过溶液旋涂方法，从含有两种间隔阳离子的前驱体溶液中沉积获得。该薄膜由取向生长的大的晶粒构成，质量高，具有很好的载流子传输特性，而且具有其中一种间隔阳离子在薄膜表面富集的梯度结构特征，有利于获得良好的耐潮湿稳定性。对于高性能杂化钙钛矿光电器件的溶液法制备具有十分重要的意义。

Description

梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜及其制备方法 技术领域
本发明属于有机-无机杂化钙钛矿材料领域，具体涉及一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜及其制备方法。
背景技术
近年来三维有机-无机杂化钙钛矿材料发展迅速，由三维有机-无机杂化钙钛矿材料制备的太阳电池最高效率已超23％，目前，研究中越来越关注钙钛矿电池的稳定性。二维钙钛矿由于含有较为疏水的间隔阳离子，因而具有比三维钙钛矿材料更好的湿稳定性。
然而，间隔阳离子会在二维钙钛矿中形成绝缘层，阻碍载流子的传输。而且，间隔阳离子的存在还会限制晶粒的长大，导致二维钙钛矿薄膜中晶界的增多，从而带来严重的载流子的复合，进而使劣化光电器件的性能。目前，避免间隔阳离子绝缘层对载流子传输的阻碍的方法，主要是使二维钙钛矿薄膜中的晶体垂直于基底取向生长，其实现的手段主要有高温(>100℃)热旋涂、使用混合溶剂(如DMF与DMSO混合)和加入易挥发添加剂(如硫氰酸铵)等。采用上述方法获得的二维钙钛矿薄膜中，间隔阳离子的分布都呈现出厚度方向向上递减的特征。考虑到间隔阳离子的疏水性特性，其在钙钛矿表面的富集将更加有利于提高薄膜的湿稳定性。所以，既具有高的电荷传输能力，又具有高的耐潮湿特性的二维杂化钙钛矿薄膜需要具备的特征是：1.薄膜由垂直于基底取向生长的大的晶粒构成；2.间隔阳离子在上表面富集，浓度分布沿薄膜厚度方向向下递减。目前，仍然没有一种方法，能够制备出上述结构的二维钙钛矿薄膜。
发明内容
本发明的目的是解决现有技术中存在的上述问题，并提供一种具有梯度结构二维 Ruddlesden-Popper杂化钙钛矿薄膜。该薄膜由取向生长的大的晶粒构成，具有良好的载流子传输特性，而且具有其中一种间隔阳离子在薄膜表面富集的梯度结构特征，有利于获得良好的耐潮湿稳定性。
本发明具体采用的技术方案如下：
一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜，该薄膜由含有两种间隔阳离子的前驱体溶液沉积获得，所述的两种间隔阳离子中一种为正丁铵，第二种为苯乙铵、苯甲铵、叔丁铵、咪唑铵、乙基吡啶铵或者异丁铵；且其中第二种间隔阳离子在薄膜表面富集，形成沿薄膜厚度方向向下递减的浓度梯度。
需要注意的是，本发明中此处所述的正丁铵、苯乙铵、苯甲铵、叔丁铵、咪唑铵、乙基吡啶铵或者异丁铵，均是指相应化合物的阳离子。
在该方案的基础上，本发明还可以进一步提供以下一种或多种优选实现方式。需要指出的是，本发明中各个优选实现方式的技术特征在没有相互冲突的前提下，均可进行相应组合。
优选的，所述的前驱体溶液中，正丁铵与第二种间隔阳离子的摩尔比为1:0.01～0.3。
优选的，所述的前驱体溶液为甲胺氢碘酸盐、两种间隔阳离子氢碘酸盐、碘化铅与有机溶剂的混合物，所述的有机溶剂为甲酰胺、二甲基亚砜、N,N-二甲基甲酰胺中的一种或者多种的混合物。
进一步的，所述的前驱体溶液中碘化铅与有机溶剂的配比为50-800毫克:1毫升。
进一步的，所述的前驱体溶液中，以摩尔比计，两种间隔阳离子氢碘酸盐：甲胺氢碘酸盐：碘化铅为2:2:3或2:3:4或2:4:5。
优选的，所述的沉积的具体过程是：将所述前驱体溶液旋涂于基底上成膜，并退火。
进一步的，基底的温度为25-70℃，前驱体溶液的温度与基底相同。
进一步的，退火温度范围为70-150℃，退火时间范围为5-20分钟。
进一步的，所述基底为旋涂有PEDOT:PSS层的ITO玻璃基底。
本发明的另一目的在于提供一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜的制备方法，其步骤如下：
首先，制备表面旋涂PEDOT:PSS层的ITO玻璃基底；
然后，将两种间隔阳离子氢碘酸盐、甲胺氢碘酸盐、碘化铅与有机溶剂混合得到前驱体溶液；所述前驱体溶液中，两种间隔阳离子中一种为正丁铵，第二种为苯乙铵、苯甲铵、叔丁铵或者异丁铵，正丁铵与第二种间隔阳离子的摩尔比为1:0.01～0.3，碘化铅与有机溶剂的配比为50-800毫克:1毫升，所述有机溶剂为甲酰胺、二甲基亚砜、N,N-二甲基甲酰胺中的一种或多种的混合物，以摩尔比计，两种间隔阳离子氢碘酸盐:甲胺氢碘酸盐：碘化铅为2:2:3或2:3:4或2:4:5；
最后，将前驱体溶液旋涂于基底上成膜，并退火；旋涂时，基底的温度为25-70℃，用于旋涂的前驱体溶液的温度与基底温度相同，退火温度范围为70-150℃，退火时间范围为5-20分钟。
本发明采用含有两种间隔阳离子的钙钛矿前驱体溶液，通过沉积，一方面获得由取向生长的大晶粒构成的二维杂化Ruddlesden-Popper杂化钙钛矿薄膜，从而获得良好的载流子传输能力；另一方面，两种间隔阳离子中的一种能够在薄膜表面的富集，形成在厚度方向向下递减的浓度梯度，有利于获得良好的耐潮湿稳定性。对于高性能杂化钙钛矿光电器件的溶液法制备具有十分重要的意义。
附图说明
图1是具有梯度结构二维Ruddlesden-Popper杂化钙钛矿薄膜横截面SEM图。
图2是苯乙铵阳离子在薄膜中分布的时间飞行二次离子质谱(TOF-SIMS)数据，左侧为薄膜的上表面，右侧为薄膜的下表面。
图3是二维Ruddlesden-Popper杂化钙钛矿薄膜储存于湿度50±5％的空气中，薄膜X射线衍射(XRD)图谱随储存时间(0天～120天)的变化。
具体实施方式
具有梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜的制备过程为：首先将ITO玻璃基底依次用洗涤剂、丙酮、异丙醇、乙醇超声洗涤5分钟后，用去离子水漂洗并烘干。经紫外-臭氧处理后，用旋涂的方法制备厚度约为25nm的PEDOT:PSS层，140℃下烘烤15分钟后取出。将两种间隔阳离子氢碘酸盐、甲胺氢碘酸盐、碘化铅与有机溶剂混合，两种间隔阳离子一种为正丁铵，第二种为苯乙铵、苯甲铵、叔丁铵或者异丁铵，正丁铵与第二种间隔阳离子的摩尔比为1:0.01～0.3；碘化铅与有机溶剂的配比为50-800毫克:1毫升；有机溶剂为甲酰胺、二甲基亚砜、N,N-二甲基甲酰胺及其混合物；间隔阳离子氢碘酸盐:甲胺氢碘酸盐：碘化铅的比例(摩尔比)为2:2:3或2:3:4或2:4:5。然后将前驱体溶液旋涂于基底上成膜，并退火。基底的温度为25-70℃，旋涂前驱体溶液的温度与基底温度相同。退火温度范围70-150℃，退火时间范围5-20分钟。
下面基于上述制备方法，通过如下实施例对本发明作进一步的详述：
实施例1：
将ITO玻璃基底依次用洗涤剂、丙酮、异丙醇、乙醇各超声洗涤5分钟后，用去离子水漂洗并烘干。烘干的ITO玻璃基底经紫外-臭氧处理后，用旋涂的方法制备厚度约为25nm的PEDOT:PSS层，140℃下烘烤15分钟后取出。将苯乙胺氢碘酸盐、正丁胺氢碘酸盐、甲胺氢碘酸盐、碘化铅混合溶解于N,N-二甲基甲酰胺中，碘化铅与N,N-二甲基甲酰胺的配比为50毫克:1毫升，(正丁胺氢碘酸盐+苯乙胺氢碘酸盐):甲胺氢碘酸盐:碘化铅(摩尔比)为2:2:3，正丁铵:苯乙胺(以离子摩尔比计)为1:0.01,搅拌过夜，获得前驱体溶液；采用溶液旋涂的方法，取25℃前驱体溶液在25℃的PEDOT:PSS覆盖ITO玻璃基底上旋涂成膜，70℃退火5分钟，得到具有梯度结构高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。薄膜横截面扫描电镜(SEM)照片如图1所示，表明该薄膜由沿着厚度方向取向生长的大晶粒构成。图2时间飞行二次离子质谱 (TOF-SIMS)数据表明，钙钛矿薄膜中两种间隔阳离子的浓度分布不同，其中苯乙铵阳离子PEA +在表面富集，即薄膜表面PEA +浓度最大，并形成沿厚度方向向下递减的浓度梯度。图3稳定性测试表明，该薄膜在湿度50±5％的空气中储存中120天，薄膜X射线衍射(XRD)图谱几乎不变，显示出良好的耐潮湿稳定性。
实施例2
将ITO玻璃基底依次用洗涤剂、丙酮、异丙醇、乙醇各超声洗涤5分钟后，用去离子水漂洗并烘干。烘干的ITO玻璃基底经紫外-臭氧处理后，用旋涂的方法制备厚度约为25nm的PEDOT:PSS层，140℃下烘烤15分钟后取出。将苯甲胺氢碘酸盐、正丁胺氢碘酸盐、甲胺氢碘酸盐、碘化铅混合溶解于甲酰胺中，碘化铅与甲酰胺的配比为800毫克:1毫升，(正丁胺氢碘酸盐+苯甲胺氢碘酸盐):甲胺氢碘酸盐:碘化铅(摩尔比)为2:4:5，正丁铵:苯甲铵(以离子摩尔比计)为1:0.3,搅拌过夜，获得前驱体溶液；采用溶液旋涂的方法，取30℃前驱体溶液在30℃的PEDOT:PSS覆盖ITO玻璃基底上旋涂成膜，150℃退火20分钟，得到具有梯度结构高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜的横截面形貌，得到的扫描电镜(SEM)照片与图1相类似，考察时间飞行二次离子质谱(TOF-SIMS)，得到的苯甲铵分布数据与图2相类似。图1与图2表明形成了具有梯度结构的高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜在湿度50±5％空气中储存120天的稳定性，薄膜X射线衍射(XRD)图谱与图3相类似，表明其良好的耐潮湿稳定性。
实施例3：
将ITO玻璃基底依次用洗涤剂、丙酮、异丙醇、乙醇各超声洗涤5分钟后，用去离子水漂洗并烘干。烘干的ITO玻璃基底经紫外-臭氧处理后，用旋涂的方法制备厚度约为25nm的PEDOT:PSS层，140℃下烘烤15分钟后取出。将叔丁胺氢碘酸盐、正丁胺氢碘酸盐、甲胺氢碘酸盐、碘化铅混合溶解于二甲基亚砜中，碘化铅与二甲基亚砜的配比为400毫克:1毫升，(正 丁胺氢碘酸盐+叔丁胺氢碘酸盐):甲胺氢碘酸盐:碘化铅(摩尔比)为2:3:4，正丁铵:叔丁铵(以离子摩尔比计)为1:0.2,搅拌过夜，获得前驱体溶液；采用溶液旋涂的方法，取70℃前驱体溶液在70℃的PEDOT:PSS覆盖ITO玻璃基底上旋涂成膜，100℃退火15分钟，得到具有梯度结构高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜的横截面形貌，得到的扫描电镜(SEM)照片与图1相类似，考察时间飞行二次离子质谱(TOF-SIMS)，得到的叔丁铵分布数据与图2相类似。图1与图2表明形成了具有梯度结构的高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜在湿度50±5％空气中储存120天的稳定性，薄膜X射线衍射(XRD)图谱与图3相类似，表明其良好的耐潮湿稳定性。
实施例4：
将ITO玻璃基底依次用洗涤剂、丙酮、异丙醇、乙醇各超声洗涤5分钟后，用去离子水漂洗并烘干。烘干的ITO玻璃基底经紫外-臭氧处理后，用旋涂的方法制备厚度约为25nm的PEDOT:PSS层，140℃下烘烤15分钟后取出。将异丁胺氢碘酸盐、正丁胺氢碘酸盐、甲胺氢碘酸盐、碘化铅混合溶解于N,N-二甲基甲酰胺/二甲基亚砜中，碘化铅与N,N-二甲基甲酰胺/二甲基亚砜的配比为600毫克:1毫升，(正丁胺氢碘酸盐+异丁胺氢碘酸盐):甲胺氢碘酸盐:碘化铅(摩尔比)为2:4:5，正丁铵:异丁铵(以离子摩尔比计)为1:0.1,搅拌过夜，获得前驱体溶液；采用溶液旋涂的方法，取60℃前驱体溶液在60℃的PEDOT:PSS覆盖ITO玻璃基底上旋涂成膜，90℃退火10分钟，得到具有梯度结构高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜的横截面形貌，得到的扫描电镜(SEM)照片与图1相类似，考察时间飞行二次离子质谱(TOF-SIMS)，得到的异丁铵分布数据与图2相类似。图1与图2表明形成了具有梯度结构的高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜在湿度50±5％空气中储存120天的稳定性，薄膜X射线衍射(XRD)图谱与图3相类似，表明其良好的耐潮湿稳定性。
实施例5：
将ITO玻璃基底依次用洗涤剂、丙酮、异丙醇、乙醇各超声洗涤5分钟后，用去离子水漂洗并烘干。烘干的ITO玻璃基底经紫外-臭氧处理后，用旋涂的方法制备厚度约为25nm的PEDOT:PSS层，140℃下烘烤15分钟后取出。将咪唑氢碘酸盐、正丁胺氢碘酸盐、甲胺氢碘酸盐、碘化铅混合溶解于N,N-二甲基甲酰胺/甲酰胺中，碘化铅与N,N-二甲基甲酰胺/甲酰胺的配比为300毫克:1毫升，(正丁胺氢碘酸盐+咪唑氢碘酸盐):甲胺氢碘酸盐:碘化铅(摩尔比)为2:3:4，正丁铵:咪唑铵(以离子摩尔比计)为1:0.05,搅拌过夜，获得前驱体溶液；采用溶液旋涂的方法，取50℃前驱体溶液在50℃的PEDOT:PSS覆盖ITO玻璃基底上旋涂成膜，120℃退火12分钟，得到具有梯度结构高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜的横截面形貌，得到的扫描电镜(SEM)照片与图1相类似，考察二次离子质谱(SIMS)，得到的咪唑铵分布数据与图2相类似。图1与图2表明形成了具有梯度结构高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。
实施例6：
将ITO玻璃基底依次用洗涤剂、丙酮、异丙醇、乙醇各超声洗涤5分钟后，用去离子水漂洗并烘干。烘干的ITO玻璃基底经紫外-臭氧处理后，用旋涂的方法制备厚度约为25nm的PEDOT:PSS层，140℃下烘烤15分钟后取出。将乙基吡啶氢碘酸盐、正丁胺氢碘酸盐、甲胺氢碘酸盐、碘化铅混合溶解于二甲基亚砜/甲酰胺中，碘化铅与二甲基亚砜/甲酰胺的配比为600毫克:1毫升，(正丁胺氢碘酸盐+苯甲胺氢碘酸盐):甲胺氢碘酸盐:碘化铅(摩尔比)为2:2:3，正丁铵:乙基吡啶铵(以离子摩尔比计)为1:0.25,搅拌过夜，获得前驱体溶液；采用溶液旋涂的方法，取65℃前驱体溶液在65℃的PEDOT:PSS覆盖ITO玻璃基底上旋涂成膜，130℃退火10分钟，得到具有梯度结构高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜的横截面形貌，得到的扫描电镜(SEM)照片与图1相类似，考察时间飞行二次离子质谱(TOF-SIMS)，得到的乙 基吡啶铵分布数据与图2相类似。图1与图2表明形成了具有梯度结构的高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜在湿度50±5％空气中储存120天的稳定性，薄膜X射线衍射(XRD)图谱与图3相类似，表明其良好的耐潮湿稳定性。
实施例7：
将ITO玻璃基底依次用洗涤剂、丙酮、异丙醇、乙醇各超声洗涤5分钟后，用去离子水漂洗并烘干。烘干的ITO玻璃基底经紫外-臭氧处理后，用旋涂的方法制备厚度约为25nm的PEDOT:PSS层，140℃下烘烤15分钟后取出。将叔丁胺氢碘酸盐、正丁胺氢碘酸盐、甲胺氢碘酸盐、碘化铅混合溶解于N,N-二甲基甲酰胺/二甲基亚砜/甲酰胺中，碘化铅与N,N-二甲基甲酰胺/二甲基亚砜/甲酰胺的配比为700毫克:1毫升，(正丁胺氢碘酸盐+叔丁胺氢碘酸盐):甲胺氢碘酸盐:碘化铅(摩尔比)为2:4:5，正丁铵:苯乙铵(以离子摩尔比计)为1:0.2,搅拌过夜，获得前驱体溶液；采用溶液旋涂的方法，取55℃前驱体溶液在55℃的PEDOT:PSS覆盖ITO玻璃基底上旋涂成膜，140℃退火20分钟，得到具有梯度结构高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜的横截面形貌，得到的扫描电镜(SEM)照片与图1相类似，考察时间飞行二次离子质谱(TOF-SIMS)，得到的叔丁铵分布数据与图2相类似。图1与图2表明形成了具有梯度结构的高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜在湿度50±5％空气中储存120天的稳定性，薄膜X射线衍射(XRD)图谱与图3相类似，表明其良好的耐潮湿稳定性。
实施例8：
将ITO玻璃基底依次用洗涤剂、丙酮、异丙醇、乙醇各超声洗涤5分钟后，用去离子水漂洗并烘干。烘干的ITO玻璃基底经紫外-臭氧处理后，用旋涂的方法制备厚度约为25nm的PEDOT:PSS层，140℃下烘烤15分钟后取出。将苯乙胺氢碘酸盐、正丁胺氢碘酸盐、甲胺氢碘酸盐、碘化铅混合溶解于N,N-二甲基甲酰胺中，碘化铅与N,N-二甲基甲酰胺的配比为200 毫克:1毫升，(正丁胺氢碘酸盐+苯乙胺氢碘酸盐):甲胺氢碘酸盐:碘化铅(摩尔比)为2:3:4，正丁铵:苯乙铵(以离子摩尔比计)为1:0.15,搅拌过夜，获得前驱体溶液；采用溶液旋涂的方法，取45℃前驱体溶液在45℃的PEDOT:PSS覆盖ITO玻璃基底上旋涂成膜，150℃退火15分钟，得到具有梯度结构高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜的横截面形貌，得到的扫描电镜(SEM)照片与图1相类似，考察时间飞行二次离子质谱(TOF-SIMS)，得到的苯乙铵分布数据与图2相类似。图1与图2表明形成了具有梯度结构的高质量二维Ruddlesden-Popper杂化钙钛矿薄膜。考察薄膜在湿度50±5％空气中储存120天的稳定性，薄膜X射线衍射(XRD)图谱与图3相类似，表明其良好的耐潮湿稳定性。

Claims (10)

  1. 一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜，其特征在于：该薄膜由含有两种间隔阳离子的前驱体溶液沉积获得，所述的两种间隔阳离子中一种为正丁铵，第二种为苯乙铵、苯甲铵、叔丁铵、咪唑铵、乙基吡啶铵或者异丁铵；且其中第二种间隔阳离子在薄膜表面富集，形成沿薄膜厚度方向向下递减的浓度梯度。
  2. 根据权利要求1所述的一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜，其特征在于所述的前驱体溶液中，正丁铵与第二种间隔阳离子的摩尔比为1:0.01～0.3。
  3. 根据权利要求1或2所述的一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜，其特征在于所述的前驱体溶液为甲胺氢碘酸盐、两种间隔阳离子氢碘酸盐、碘化铅与有机溶剂的混合物，所述的有机溶剂为甲酰胺、二甲基亚砜、N,N-二甲基甲酰胺中的一种或者多种的混合物。
  4. 根据权利要求3所述的一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜，其特征在于所述的前驱体溶液中碘化铅与有机溶剂的配比为50-800毫克:1毫升。
  5. 根据权利要求3所述的一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜，其特征在于所述的前驱体溶液中，以摩尔比计，两种间隔阳离子氢碘酸盐：甲胺氢碘酸盐：碘化铅为2:2:3或2:3:4或2:4:5。
  6. 根据权利要求1所述的一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜，其特征在于所述的沉积的具体过程是：将所述前驱体溶液旋涂于基底上成膜，并退火。
  7. 根据权利要求6所述的一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜，其特征在于旋涂时，基底的温度为25-70℃，前驱体溶液的温度与基底相同。
  8. 根据权利要求6所述的一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜，其特征在于退火温度范围为70-150℃，退火时间范围为5-20分钟。
  9. 根据权利要求6所述的一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜， 其特征在于所述基底为旋涂有PEDOT:PSS层的ITO玻璃基底。
  10. 一种梯度结构特征的二维Ruddlesden-Popper杂化钙钛矿薄膜的制备方法，其特征在于，步骤如下：
    首先，制备表面旋涂PEDOT:PSS层的ITO玻璃基底；
    然后，将两种间隔阳离子氢碘酸盐、甲胺氢碘酸盐、碘化铅与有机溶剂混合得到前驱体溶液；所述前驱体溶液中，两种间隔阳离子中一种为正丁铵，第二种为苯乙铵、苯甲铵、叔丁铵或者异丁铵，正丁铵与第二种间隔阳离子的摩尔比为1:0.01～0.3，碘化铅与有机溶剂的配比为50-800毫克:1毫升，所述有机溶剂为甲酰胺、二甲基亚砜、N,N-二甲基甲酰胺中的一种或多种的混合物，以摩尔比计，两种间隔阳离子氢碘酸盐:甲胺氢碘酸盐：碘化铅为2:2:3或2:3:4或2:4:5；
    最后，将前驱体溶液旋涂于基底上成膜，并退火；旋涂时，基底的温度为25-70℃，用于旋涂的前驱体溶液的温度与基底温度相同，退火温度范围为70-150℃，退火时间范围为5-20分钟。
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