WO2015109647A1 - 一种两性分子改性的钙钛矿光电功能材料及其应用 - Google Patents

一种两性分子改性的钙钛矿光电功能材料及其应用 Download PDF

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WO2015109647A1
WO2015109647A1 PCT/CN2014/073653 CN2014073653W WO2015109647A1 WO 2015109647 A1 WO2015109647 A1 WO 2015109647A1 CN 2014073653 W CN2014073653 W CN 2014073653W WO 2015109647 A1 WO2015109647 A1 WO 2015109647A1
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functional material
perovskite
organic
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photoelectric functional
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韩宏伟
梅安意
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华中科技大学
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Priority to JP2016520247A priority Critical patent/JP6151447B2/ja
Priority to EP14880101.2A priority patent/EP3098871B1/en
Publication of WO2015109647A1 publication Critical patent/WO2015109647A1/zh
Priority to US14/979,477 priority patent/US10059875B2/en

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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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Definitions

  • the invention relates to a M z A y BX z+y+2 perovskite-based photoelectric functional material and a preparation method thereof, and belongs to the technical field of electronic devices.
  • a perovskite material having an eight-eighth structure has its characteristic crystal structure and also exhibits excellent properties. These materials have high carrier mobility, high porosity, and a wide spectral response range, with strong absorption in the range of 300 nm to 800 nm. In addition, electrons and holes have a longer lifetime in the ABX 3 perovskite material, and the carrier diffusion length reaches 100 nm, making charge separation easier.
  • the preparation method has the advantages of simple preparation method, wide source of materials and low cost, and the obtained photoelectric functional material has excellent photoelectric performance and good stability, and the efficiency and stability of the battery are obviously improved in the field of solar cells based on perovskite materials. The advantages have great industrial application prospects.
  • an organic amphiphile-modified M z A y BX z+y+2 perovskite-based photoelectric functional material is provided, which is based on an ABX3 perovskite material, organic
  • the amphiphilic molecule M is a modified component, and its chemical formula can be expressed as M x A y BX x+y+2 .
  • R2 in the amphiphilic group R1-R-R2 is at least one of -COOH, -OSiOH, -0 3 P0H , -0 2 S0H and the like.
  • R in the amphiphile R1-R-R2 is a type of organic group, and may be, for example, a linear or branched or halogenated alkyl group in C1-C30; C3-C12 Cycloalkyl; heterocyclic ring in C1-C12; alkenyl group in C2-C8; alkynyl group in C2-C8; aryl group in C6-C12; aralkyl group in C8-C30; C6-C30 An alkylaryl group; an isoaryl group in C1-C12; an alkyl heteroaryl group in C6-C30; an alkyl heterocycle in C6-C30, and the like.
  • a in the M x A y BX x+y+2 photoelectric functional material is at least one of methylamine, formazan, hydrazine and the like.
  • B in the M x A y BX x+y+2 photoelectric functional material is at least one of lead, tin, copper, bismuth and the like.
  • X in the M x A y BX x+y+2 photoelectric functional material is at least one of chlorine, bromine, iodine and the like.
  • M x A y BX x+y+2 photoelectric functional material in a solar cell, wherein M x A y BX x+y+2 is used as light in a solar cell Absorbent layer, n-type or p-type material.
  • an application of an M x A y BX x+y+2 optoelectronic functional material in other fields such as LEDs, electronic components, and the like is provided.
  • a method of preparing the above-described electrically functional material is provided, and specifically includes:
  • amphiphilic molecule M with hydriodic acid in a mixed bath in ice water, spin-dry, and wash the precipitate with diethyl ether to obtain an iodate.
  • the iodate, the methylamine iodide MAI and the Pbl2 are weighed stoichiometrically, and an appropriate amount of gamma-martactone is added thereto, and stirred to sufficiently react to obtain a precursor solution.
  • the invention has the significant advantages of: improving the crystal form of the ABX3 perovskite material by using a low-cost, wide-ranging organic amphiphilic molecule, thereby greatly improving the crystallization property, thereby significantly improving the photoelectricity of the solar cell based on the perovskite material. Conversion efficiency and stability.
  • the material preparation method of the invention is simple, the equipment used is simple, the materials used are widely sourced, the cost is low, and the obtained material has excellent photoelectric performance and stability.
  • M in M x A y BX x+y+2 is 4-aminobutyric acid
  • A is methylamine
  • B is lead
  • X is chlorine
  • x is 0.1
  • y 0.95
  • the photoelectric conversion efficiency of 11% is obtained, which is much higher than that of the same battery, and exhibits good stability.
  • the M x A y BX x+y+2 photoelectric functional material of the present invention has a good industrial application prospect.
  • the ABX 3 perovskite-based photoelectric functional material modified by the organic amphiphile disclosed by the invention is prepared by using the whole solution method and used in the solar cell, and the crystallization property thereof is greatly improved compared with the unmodified material, and the photoelectricity is improved. Conversion efficiency and stability show significant advantages. Under the same conditions, when the M x A y BX x+ y 2 photoelectric functional material of the present invention is applied to a mesoscopic solar cell based on a carbon counter electrode, the photoelectric conversion efficiency and stability obtained are significantly higher than that. The efficiency of applying unmodified material ABX3 to such batteries has previously been reported.
  • an organic amphiphilic modified ABX3 perovskite-based photoelectric functional material is based on an ABX3 perovskite material, and the organic amphiphilic molecule M is a modified component, and the chemical formula can be expressed as M z A y BX z+y+2 .
  • R2 in the amphiphile R1-R-R2 may be at least one of -COOH, -OSiOH, -0 3 P0H , -0 2 S0H and the like.
  • R in the amphoteric molecule R1-R-R2 is an organic group, and may be various organic groups, such as linear, or branched, or substituted alkyl groups in C1-C30; a cycloalkyl group in C12; a heterocyclic ring in C1-C12; an alkenyl group in C2-C8; an alkynyl group in C2-C8; an aryl group in C6-C12; an aralkyl group in C8-C30; C6 - an alkylaryl group in C30; an isoaryl group in C1-C12; an alkylisoaryl group in C6-C30; an alkyl heterocyclic ring in C6-C30, etc., or other organic group.
  • organic groups such as linear, or branched, or substituted alkyl groups in C1-C30; a cycloalkyl group in C12; a heterocyclic ring in C1-C12; an alkeny
  • a in the M z A y BX z+y+2 photoelectric functional material is preferably one of methylamine, formazan, hydrazine, and the like.
  • B in the M z A y BX z+y+2 photoelectric functional material is preferably one of lead, tin, copper, bismuth or the like.
  • X in the M z A y BX z+y+2 photoelectric functional material is preferably at least one of chlorine, bromine, iodine and the like.
  • the content z of M in the photoelectric functional material of M z A y BX z+y+2 is in the range of 0 ⁇ z ⁇ 0.5, and the content y of A is 0 ⁇ y ⁇ l, and y + z ⁇ l .
  • short-chain ammonium cations such as methylamine, formazan, hydrazine and the like are filled into the voids of the metal halide BX2 octahedron to form a three-dimensional perovskite material;
  • a short-chain ammonium cation or a monovalent ion such as ruthenium ion is filled into the void of the apex of the metal octahedron to form a three-dimensional perovskite layer (the thickness of which is determined by the stoichiometry of the amphiphilic M and the monovalent ion)
  • the ratio is determined, and the amphiphilic M forms an organic layer between the three-dimensional perovskite layer and the layer, and finally forms a modified perovskite material in which a plurality of layers of perovskite sheets and amphiphilic molecules are alternately stacked.
  • the method for preparing an organic amphiphilic modified ABX3 perovskite-based photoelectric functional material comprises the following steps:
  • the amphoteric molecule M and the hydroiodic acid may be sufficiently reacted in a mixed bath of ice water, and the mixture is subjected to rotary evaporation, and the precipitate is washed with diethyl ether to obtain iodic acid. salt; (2) taking an appropriate amount of the halide and the methyl iodide to react with 131 2 to obtain a perovskite precursor solution. Specifically, it is preferred to weigh the iodate, the methyl iodide MAI and the Pbl2, respectively, in a stoichiometric ratio. Adding an appropriate amount of gamma lactone to the mixture and stirring it to fully react to obtain a precursor solution;
  • the perovskite material can be obtained by drying the precursor solvent.
  • the amphiphilic 4-aminobutyric acid GABA and hydriodic acid were sufficiently reacted in a mixing bath of ice-water at a stoichiometric ratio of 1:1, and the precipitate was rotary-screwed, and the precipitate was washed with diethyl ether to obtain (GABA)I.
  • GABA 4-aminobutyric acid
  • hydriodic acid was sufficiently reacted in a mixing bath of ice-water at a stoichiometric ratio of 1:1, and the precipitate was rotary-screwed, and the precipitate was washed with diethyl ether to obtain (GABA)I.
  • weigh (GABA)I, iodide methylamine MAI, Pbl2 according to stoichiometric ratio add appropriate amount of gamma lactone to it, stir and fully react to obtain (GABA)o .iMAo.95Pbl3.05 precursor
  • the amphiphilic 4-aminobutyric acid GABA and hydrochloric acid were sufficiently reacted in a water-mixing bath at a stoichiometric ratio of 1:1, and the precipitate was rotary-screwed, and the precipitate was washed with diethyl ether to obtain (GABA)CI.
  • GABA 4-aminobutyric acid
  • hydrochloric acid was sufficiently reacted in a water-mixing bath at a stoichiometric ratio of 1:1, and the precipitate was rotary-screwed, and the precipitate was washed with diethyl ether to obtain (GABA)CI.
  • GABA iodide methylamine MAI, Pbl2
  • add appropriate amount of DMF to it, and stir it to fully react to obtain (GABA)o.06MAo.97Pbl2.
  • the 97Clo.06 precursor solution was filled in a mesoscopic solar cell based on a carbon counter electrode and dried at 70 °
  • the iBra.95 precursor solution was filled in a mesoscopic solar cell based on a carbon counter electrode and dried at 60 ° C. The efficiency of the tested battery was 9.8%.
  • methyl iodide may be replaced by methylamine chloride, methyl bromide, etc.
  • lead iodide may be replaced by lead bromide, lead chloride, cesium iodide, tin iodide, and the like.
  • the stoichiometric ratio is not limited to the above range, and only needs to satisfy 0 ⁇ z ⁇ 0.5, 0 ⁇ y ⁇ l, y+z ⁇ l.
  • the perovskite-based photoelectric functional material of the present invention can be used in a solar cell, and as a light absorbing layer in a solar cell, an n-type or p-type material can also be used for an LED or an electronic component as a semiconductor material.

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Abstract

一种有机两性分子改性的MzAyBXz+y+2钙钛矿基光电功能材料及其制备方法和应用，该功能材料是以ABX3钙钛矿材料为基体，以有机两性分子M为改性成分，其化学通式表示为MzAyBXz+y+2。所使用的基体材料与改性材料成本低廉，原料丰富；此外，制备方法可采用全溶液法，制备工艺简单，无需昂贵的设备仪器，同时很好地改善了所得钙钛矿材料的结晶性能，用其制得的太阳能电池的光电转换效率与稳定性得到大幅度提升。

Description

一种两性分子改性的钙钛矿光电功能材料及其应用 【技术领域】
本发明涉及一种 MzAyBXz+y+2钙钛矿基光电功能材料及其制备方法， 属于电子 器件技术领域。
【背景技术】
随着人类社会发展对能源需求的与日俱增与传统化石能源的日益减少，未来 面临一个很大的挑战就是需要找一种可再生的新能源来代替传统的化石能源。目 前正在研究利用的新能源包括风能， 地热， 核能， 太阳等。 但是风能和地热有着 很大的地域限制， 核能存在较大的安全隐患且原料不可再生。太阳能以其取之不 尽，用之不竭而又不产生污染等特点而受到重视。对太阳能的利用主要有光热转 换， 光化学转换和光电转换等； 由于种种原因， 光热转换与光化学转换的推广使 用受到一定的限制，光电转换即太阳能电池以独特的优势而被广泛研究。 目前市 场上占主导地位的太阳能电池为硅基太阳能电池，但其制备成本较高，工艺复杂， 因此寻找成本低廉的， 制备工艺简单的光电转换材料就很有必要。
钙钛矿材料 ABX3作为一种光电性能优良的材料， 高的光电转换效率， 而迅 速成为焦点。 具有八8^结构的钙钛矿材料具有其特有的晶体结构， 同时也表现 出优异的性能。这类材料有很高的载流子迁移率， 高的空穴率以及较宽的光谱响 应范围， 在 300nm~800nm的范围内有很强的吸收。 此外， 电子与空穴等在 ABX3 钙钛矿材料中的寿命较长，载流子扩散长度达到 lOOnm，使得电荷分离更加容易。 因此， 当基于 ABX3钙钛矿材料， 并采用全溶液法的太阳能电池于 2012年 8月报 道出 9.7%的光电转换效率之后， 迅速成为研究的热点， 在短短一年多的时间内， 通过工艺的改变与控制， 其效率从 9.7%迅速提升到 14.1%乃至 16.4%。 这些研究 结果为低成本， 高效率的太阳能电池提供一片广阔的空间。
虽然 八8^钙钛矿材料应用在太阳能电池中取得了重大进展， 但是采用全溶 液法时其结晶形态存在的不足大大制约了基于该类材料的太阳能电池的效率与 稳定性。利用真空气相沉积等手段虽然有助于控制其结晶，但却大幅度提升了成 本， 制约了其应用。
【发明内容】 本发明的目的在于提供一种有机两性分子改性的 MzAyBXz+y+2钙钛矿基光电 功能材料。 本发明制备方法简单， 使用的材料来源广泛， 成本低廉， 所制得的光 电功能材料光电性能优良，稳定性好，在基于钙钛矿材料的太阳能电池领域对提 升电池的效率与稳定性有着明显的优势， 有很大的工业化应用前景。
为实现上述目的， 按照本发明的一个方面， 提供一种有机两性分子改性的 MzAyBXz+y+2钙钛矿基光电功能材料， 其以 ABX3钙钛矿材料为基体， 有机两性分 子 M为改性成分， 其化学通式可以表示为 MxAyBXx+y+2。
进一步地， MxAyBXx+y+2光电功能材料中的两性分子 M可以表示为 R1-R-R2, 两性分子 R1-R-R2中的 R1至少为 -NH2， -NH-C(NH2)=NH , -N=CH-NH2等中的一种。
进一步地，两性分子 R1-R-R2中的 R2至少为 -COOH， -OSiOH , -03P0H , -02S0H 等中的一种。
进一步地， 两性分子 R1-R-R2中的 R为各类有机基团， 例如可以为 C1-C30中 的一种线性的、 或者带支链的、 或者卤代的烷基； C3-C12 中的环烷基； C1-C12 中的杂环； C2-C8中的烯基； C2-C8中的炔基； C6-C12中的芳基； C8-C30中的芳 烷基； C6-C30中的烷基芳香基； C1-C12中的异芳基； C6-C30中的烷基异芳基； C6-C30中的烷基杂环等中至少一种。
进一步地， 所述的 MxAyBXx+y+2光电功能材料中的 A为甲胺， 甲脒， 铯等中至 少一种。
进一步地， 所述的 MxAyBXx+y+2光电功能材料中的 B为铅， 锡， 铜， 锗等中至 少一种。
进一步地， 所述的 MxAyBXx+y+2光电功能材料中的 X为氯， 溴， 碘等中至少一 种。
按照本发明的另一方面， 提供一种上述 MxAyBXx+y+2光电功能材料在太阳能电 池中的应用， 其中， MxAyBXx+y+2作为太阳能电池中的光吸收层， n型或 p型材料。
按照本发明的又一方面， 提供一种 MxAyBXx+y+2光电功能材料在 LED、 电子元 器件等其他领域的应用。
按照本发明的再一方面， 提供一种种上述 电功能材料的制备方 法， 具体包括：
( 1 ) 将两性分子与氢卤酸反应得到卤酸盐； ( 2 ) 取适量卤酸盐和碘化甲胺一起与 1312反应得到钙钛矿前驱体溶液； ( 3 ) 烘干前驱体溶剂即可得到钙钛矿材料。
具体地，可以优选将两性分子 M与氢碘酸在在冰水混合浴中充分反应，旋蒸， 用乙醚清洗沉淀， 得到碘酸盐。
优选按化学计量比分别称量碘酸盐， 碘化甲胺 MAI以及 Pbl2， 向其中加入适 量伽马丁内酯， 搅拌使其充分反应， 得到前驱体溶液。
本发明的显著优点在于： 利用成本低廉， 来源广泛的有机两性分子来改善 ABX3 钙钛矿材料的结晶形态， 使其结晶性能大幅度提升， 从而显著提高了基于 钙钛矿材料的太阳能电池的光电转换效率和稳定性。
本发明所述材料制备方法简单， 所用设备简单， 使用的材料来源广泛， 成本 低廉， 同时得到的材料有优异的光电性能和稳定性。
当 MxAyBXx+y+2中的 M为 4-氨基丁酸， A为甲胺， B为铅， X为氯， x取值 0.1， y取值 0.95的时候， 将其应用于已报道的基于碳对电极的介观太阳能电池中时， 得到 11%的光电转换效率， 远高于同种电池的效率， 同时表现出很好地稳定性。 与已有的 ABX3钙钛矿材料相比， 本发明所述的 MxAyBXx+y+2光电功能材料有很好 的工业应用前景。
本发明公布的以有机两性分子改性的 ABX3钙钛矿基光电功能材料， 利用全 溶液法制备并用在太阳能电池中时， 与未改性材料相比，其结晶性能有着大幅度 改善， 光电转换效率和稳定性表现出了明显的优势。在相同的条件下， 将本发明 所述的 MxAyBXx+y— 2光电功能材料应用于基于碳对电极的介观太阳能电池中时，得 到的光电转换效率和稳定性显著高于此前报道的将未改性材料 ABX3应用于此类 电池中的效率。
【具体实 式】
为了使本发明的目的、 技术方案及优点更加清楚明白， 以下结合实施例， 对 本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释 本发明， 并不用于限定本发明。
本实施例的一种有机两性分子改性的 ABX3钙钛矿基光电功能材料， 以 ABX3 钙钛矿材料为基体， 有机两性分子 M 为改性成分， 其化学通式可以表示为 MzAyBXz+y+2。 MxAyBXx+y+2光电功能材料中的两性分子 M可以表示为 R1-R-R2, 其中， 两性 分子 R1-R-R2中的 R1可以为 -NH2， -NH-C(NH2)=NH , -N=CH-NH2等中的至少一种。
两性分子 R1-R-R2中的 R2可以为 -COOH， -OSiOH , -03P0H , -02S0H等中的至 少一种。
本实施例中， 两性分子 R1-R-R2中的 R为有机基团， 可以是各类有机基团， 例如 C1-C30中的线性的、或者带支链的、或者 代的烷基； C3-C12中的环烷基； C1-C12中的杂环； C2-C8中的烯基； C2-C8中的炔基； C6-C12中的芳基； C8-C30 中的芳烷基； C6-C30中的烷基芳香基； C1-C12中的异芳基； C6-C30中的烷基异 芳基； C6-C30中的烷基杂环等， 也可以是其他有机基团。
本实施例中， MzAyBXz+y+2光电功能材料中的 A优选为甲胺， 甲脒， 铯等中的 一种。
本实施例中， MzAyBXz+y+2光电功能材料中的 B优选为铅， 锡， 铜， 锗等中的 一种。
本实施例中， MzAyBXz+y+2光电功能材料中的 X优选为为氯， 溴， 碘等中的至 少一种。
MzAyBXz+y+2光电功能材料中 M的含量 z的取值范围为， 0<z≤0.5， A的含量 y 的取值为 0<y≤l， 并且 y+z≥l。 优选 z=0.01~0.1， y=0.95~l。
在不使用两性分子改性时， 短链的铵阳离子如甲胺， 甲脒， 铯等一价离子填 入到金属卤化物 BX2八面体共顶点连接的空隙中形成三维的钙钛矿材料； 当加入 两性分子之后，短链的铵阳离子或者铯离子等一价离子填入到金属 ¾化物八面体 共顶点连接的空隙中形成三维钙钛矿层 （其厚度由两性分子 M与一价离子的化 学计量比确定）， 而两性分子 M则在该三维钙钛矿层与层之间形成有机层， 最终 形成多层钙钛矿片层与两性分子交替堆积的改性钙钛矿材料。有机两性分子的存 在， 大大改善了材料的大面积成膜性能以及其稳定性， 同时优化了其光电性能。
本实施例的一种有机两性分子改性的 ABX3钙钛矿基光电功能材料的制备方 法， 包括如下步骤：
( 1 )将两性分子与氢卤酸反应得到卤酸盐， 具体地， 可以优选将两性分子 M与氢碘酸在在冰水混合浴中充分反应， 旋蒸， 用乙醚清洗沉淀， 得到碘酸盐； ( 2 ) 取适量其卤酸盐和碘化甲胺一起与 1312反应得到钙钛矿前驱体溶液， 具体地， 优选按化学计量比分别称量碘酸盐， 碘化甲胺 MAI 以及 Pbl2， 向其中 加入适量伽马丁内酯， 搅拌使其充分反应， 得到前驱体溶液；
( 3 ) 烘干前驱体溶剂即可得到钙钛矿材料。
实施例 1
本实施例中， 将两性分子 4-氨基丁酸 GABA与氢碘酸按照化学计量比 1:1在 冰水混合浴中充分反应，旋蒸，用乙醚清洗沉淀，得到（GABA)I。取 z=0.1， y=0.95 , 按化学计量比分别称量 (GABA)I， 碘化甲胺 MAI， Pbl2， 向其中加入适量伽马丁内 酯， 搅拌使其充分反应， 得到 (GABA)o.iMAo.95Pbl3.05前驱体溶液。 取适量填充于 基于碳对电极的介观太阳能电池中， 并在 50°C烘干， 测试得到的电池的光电转 换效率， 达到 11%。
实施例 2
本实施例中， 将两性分子 4-氨基丁酸 GABA与盐酸按照化学计量比 1:1在冰 水混合浴中充分反应， 旋蒸， 用乙醚清洗沉淀， 得到 (GABA)CI。取 z=0.06， y=0.97 按化学计量比分别称量 (GABA)CI， 碘化甲胺 MAI， Pbl2， 向其中加入适量 DMF， 搅拌使其充分反应， 得到 (GABA)o.06MAo.97Pbl2.97Clo.06前驱体溶液， 取适量填充于 基于碳对电极的介观太阳能电池中， 并在 70°C烘干， 测试得到的电池的光电转 换效率， 达到 10.3%。
实施例 3
本实施例中， 将两性分子 4-氨基丁酸 GABA与氢碘酸按照化学计量比 1： 1在 冰水混合浴中充分反应， 旋蒸， 用乙醚清洗沉淀， 得到（GABA)I， 取 z=0.1， y=0.95 分别称量 (GABA)I， 溴化甲胺 MABr， Pbl2， 向其中加入适量的伽马丁内酯， 搅拌 使其充分反应， 得到 （GABA) o.iMAo.95Pbl2.iBra.95前驱体溶液， 取适量填充于基 于碳对电极的介观太阳能电池电池中， 并在 60°C下烘干， 测试得到的电池的效 率， 达至 Ij 9.8%。
上述实施实例中， 两性分子并不限于 4-氨基丁酸 GABA， 还可以为其他材料， 诸如 6-氨基己酸， HOOC-CH2-CH=CH-CH2-NH2， 4-胍基丁酸， 对氨基苯磺酸等； 一 般地，两性分子 M表示为 R1-R-R2,其中， Rl ¾-NH2, -NH-C(NH2)=NH或 -N=CH-NH2 中的至少一禾中， R2为- C00H， -OSiOH, -03P0H或 -02S0H中的至少一种， R为有 机基团。
另外， 碘化甲胺可以替换为氯化甲胺， 溴化甲胺等， 碘化铅可以替换为溴化 铅， 氯化铅， 碘化锗， 碘化锡等。 同时化学计量比并不限于上述范围， 只需满足 0<z≤0.5 , 0<y≤l， y+z≥l即可。
本发明的钙钛矿基光电功能材料可以用于太阳能电池中， 作为太阳能电池中 的光吸收层， n型或 p型材料， 也可以用于 LED、 电子元器件， 作为半导体材料。
本领域的技术人员容易理解， 以上所述仅为本发明的较佳实例而已， 并不用 以限制本发明， 凡在本发明的精神和原则之内所做的任何修改，等同替换和改进 等， 均应包含在本发明的保护范围之内。

Claims

1、 一种有机两性分子改性 MzAyBXz+y+2钙钛矿基光电功能材料， 其特征在于， 该功能材料是以 ABX3钙钛矿材料为基体， 以有机两性分子 M为改性成分， 其化 学通式表示为 MzAyBXz+y+2。
2、 根据权利要求 1所述的一种有机两性分子改性的 MzAyBXz+y+2钙钛矿基光 电功能材料， 其特征在于， A为一价离子， B为二价金属离子， X为卤素离子。
3、 根据权利要求 1或 2所述的一种有机两性分子改性的 ABX3钙钛矿基光电 功能材料， 其特征在于， A为有机铵阳离子或者碱金属离子， 优选为甲胺， 甲脒 或铯中的至少一种。
4、 根据权利要求 1-3中任一项所述的一种有机两性分子改性的 ABX3钙钛矿 基光电功能材料， 其特征在于， B为铅， 锡， 铜， 锗中的至少一种。
5、 根据权利要求 1-4中任一项所述的一种有机两性分子改性的 ABX3钙钛矿 基光电功能材料，其特征在于，所述两性分子 M表示为 R1-R-R2,其中， R1为 -NH2， -NH-C(NH2)=NH或 -N=CH-NH2中的至少一种， R2为- COOH， -OSiOH , -03P0H或 -02S0H中的至少一种， R为有机基团。
6、 根据权利要求 5所述的一种有机两性分子改性的 ABX3钙钛矿基光电功能 材料， 其特征在于， 所述 R为 C1-C30中的一种线性的、 或者带支链的、 或者卤 代的烷基； C3-C12中的环烷基，或 C1-C12中的杂环，或 C2-C8中的烯基，或 C2-C8 中的炔基， 或 C6-C12中的芳基， 或 C6-C30中的芳烷基， 或 C6-C30中的烷基芳 香基， C1-C12中的异芳基， C6-C30中的烷基异芳基， C6-C30中的烷基杂环中的 至少一种。
7、 根据权利要求 1-6中任一项所述的一种有机两性分子改性的 ABX3钙钛矿 基光电功能材料， 其特征在于， X为氯， 溴， 碘中的至少一种。
8、 根据权利要求 1-7中任一项所述的一种有机两性分子改性的 ABX3钙钛矿 基光电功能材料， 其特征在于， M的含量 z的取值范围为 0<z≤0.5， A的含量 y 的取值为 0<y≤l， 并且 y+z≥l。
9、 一种有机两性分子改性的 MzAyBXz+y+ 钛矿基光电功能材料的制备方法， 具体包括如下步骤：
( 1 ) 将两性分子与氢卤酸反应得到卤酸盐； ( 2 ) 取适量卤酸盐和碘化甲胺一起与 1312反应得到钙钛矿前驱体溶液；
( 3 ) 烘干前驱体溶剂即可得到钙钛矿材料。
10、 权利要求 1-8中任一项所述的有机两性分子改性的 MzAyBXz+y+ 钛矿基 光电功能材料在太阳能电池中的应用，其中， 该电功能材料作为太阳能电池中的 光吸收层， n型或 p型材料； 或作为半导体材料在 LED或电子元器件中的应用。
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