Perovskite photoelectric functional material modified with amphipathic molecule, and methods for preparing and using the same

Abstract

A perovskite-based photoelectric functional material having a general formula M.sub.zA.sub.yBX.sub.z+y+2. The matrix of the photoelectric functional material is a perovskite material ABX.sub.3, M is an organic amphipathic molecule used as a modification component of the matrix, 0<z?0.5, 0<y?1, and y+z?1.

Claims

1. A photoelectric material, having a general formula M.sub.zA.sub.yBX.sub.z+y+2, wherein: a matrix of the photoelectric functional material is a perovskite material ABX.sub.3; A is a monovalent ion; B is a divalent metal ion; X is a halide ion; 0<z?0.5; 0<y?1; y+z?1; and M is an organic amphipathic molecule used as a modification component of the matrix, and has a formula of R.sup.1RR.sup.2, wherein R.sup.1 is selected from the group consisting of NH.sub.2, NHC(NH.sub.2)?NH and N?CHNH.sub.2, R.sup.2 is selected from the group consisting of COOH, OSiOH, O.sub.3POH and O.sub.2SOH, and R is an organic group.

2. The material of claim 1, wherein A is an organic amine cation or an alkali metal ion, and A is selected from the group consisting of methylammonium ion, formamidine ion, and cesium ion.

3. The material of claim 1, wherein B is selected from the group consisting of lead, tin, copper and germanium.

4. The material of claim 2, wherein B is selected from the group consisting of lead, tin, copper and germanium.

5. The material of claim 1, wherein R is selected from the group consisting of linear alkyl, branched alkyl and halogenated C.sub.1-30-alkyl, C.sub.3-12-cycloalkyl, C.sub.1-12-heterocycle, C.sub.2-8-alkenyl, C.sub.2-8-alkynyl, C.sub.6-12-aryl, C.sub.6-30-aralkyl, C.sub.6-30-alkylaryl, C.sub.1-12-heteroaryl, C.sub.6-30-alkyl heteroaryl and C.sub.6-30-alkyl heterocycle.

6. The material of claim 1, wherein X is selected from the group consisting of chlorine, bromine and iodine.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) For further illustrating the invention, experiments detailing a perovskite-based photoelectric functional material M.sub.zA.sub.yBX.sub.z+y+2 and a preparation method thereof are described below. It should be noted that the following examples are intended to describe and not to limit the invention.

(2) According to one embodiment of the invention, there is provided a perovskite-based photoelectric functional material modified with an organic amphipathic molecule, expressed by a general formula M.sub.zA.sub.yBX.sub.z+y+2, where M is an organic amphipathic molecule used as a modification component with a perovskite material ABX.sub.3 as a matrix.

(3) The organic amphipathic molecule M is expressed by R1-RR2, R1 is selected from a group consisting of NH.sub.2, NHC(NH.sub.2)?NH and N?CHNH.sub.2, and R2 is selected from a group consisting of COOH, OSiOH, O.sub.3POH and O.sub.2SOH.

(4) In this embodiment, R is an organic group and is selected from a group consisting of linear alkyl, branched alkyl and halogenated alkyl of C1-C30, cycloalkyl of C3-C12, heterocycle of C1-C12, alkenyl of C2-C8, alkynyl of C2-C8, aryl of C6-C12, aralkyl of C6-C30, alkylaryl of C6-C30, heteroaryl of C1-C12, alkyl heteroaryl of C6-C30 and alkyl heterocycle of C6-C30.

(5) In this embodiment, A is selected from a group consisting of methylamine, formamidine and cesium preferably.

(6) In this embodiment, B is selected from a group consisting of lead, tin, copper and germanium preferably.

(7) In this embodiment, X is selected from a group consisting of chlorine, bromine and iodine preferably.

(8) In the photoelectric functional material M.sub.xA.sub.yBX.sub.x+y+2, 0<z?0.5, 0<y?1, and y+z?1, and z=0.01-0.1 and y=0.95-1 preferably.

(9) When no amphipathic molecule is introduced, monovalent ions such as short-chained amine cations (such as methylamine and formamidine) and cesium ions enter gaps among co-vertex connected octahedrons of a metal halide BX.sub.2 to form a 3D perovskite material. When an amphipathic molecule is introduced, short-chained amine cations or cesium ions enter gaps among co-vertex connected octahedrons of the metal halide to form 3D perovskite layers (thickness of each perovskite layer is determined by molar ratio between the amphipathic molecule and the monovalent ion), and an organic layer is generated between every two 3D perovskite layers to obtain a modified perovskite material with perovskite layers and organic layers overlapped alternatively. Film quality in a large area and stability of the material is significantly improved and photovoltaic properties thereof are optimized due to the existence of organic amphipathic molecules.

(10) According to one embodiment of the invention, there is provided a preparation method of a perovskite-based photoelectric functional material modified with an organic amphipathic molecule, comprising steps of:

(11) 1) Obtaining a halate by an amphipathic molecule reacting with halogen acid; Specifically and preferably, an iodate is obtained by an amphipathic molecule M fully reacting with hydroiodic acid into an ice-water bath, rotary evaporation, and washing the precipitate with diethyl ether.

(12) 2) Obtaining a perovskite precursor solution by an appropriate amount of the halate and methylamine iodide reacting with PbI.sub.2;

(13) Specifically and preferably, a precursor solution is obtained by adding an appropriate amount of ?-butyrolactone into iodate, methylamine iodide and PbI.sub.2 weighted respectively by molar ratio and stirring the mixture for fully reaction.

(14) 3) Drying the perovskite precursor solution thereby obtaining the perovskite-based photoelectric functional material.

Example 1

(15) In this example, an amphipathic molecule 4-aminobutyric acid (GABA) is fully reacted with hydroiodic acid into an ice-water bath with a molar ratio of 1:1. After rotary evaporation, the precipitate is washed by diethyl ether thoroughly and the (GABA)I powder is obtained. Then, (GABA)I, methylamine iodide and PbI.sub.2 are mixed with a molar ratio of 0.1:0.95:1 and an appropriate amount of ?-butyrolactone is added and stirred for fully reaction to obtain the (GABA).sub.0.1MA.sub.0.95PbI.sub.3.05 precursor solution. An appropriate amount of the precursor solution is filled into a carbon-materials-based counter electrode mesoscopic solar cell and dried at 50? C. and photovoltaic conversion efficiency of the solar cell is up to 11%.

Example 2

(16) In this example, an amphipathic molecule 4-aminobutyric acid (GABA) is fully reacted with hydrochloric acid into an ice-water bath with a molar ratio of 1:1. After rotary evaporation, the precipitate is washed by diethyl ether thoroughly and the (GABA)Cl powder is obtained. Then, (GABA)Cl, methylamine iodide and PbI.sub.2 are mixed with a molar ratio of 0.06:0.97:1 and an appropriate amount of DMF is added and stirred for fully reaction to obtain the (GABA).sub.0.06MA.sub.0.97PbI.sub.2.97Cl.sub.0.06 precursor solution. An appropriate amount of the precursor solution is filled into a carbon-materials-based counter electrode mesoscopic solar cell and dried at 70? C. and photovoltaic conversion efficiency of the solar cell is up to 11%.

Example 3

(17) In this example, an amphipathic molecule 4-aminobutyric acid (GABA) is fully reacted with hydroiodic acid into an ice-water bath with a molar ratio of 1:1. After rotary evaporation, the precipitate is washed by diethyl ether thoroughly and the (GABA)I powder is obtained. Then, (GABA)I, methylamine bromide and PbI.sub.2 are mixed with a molar ratio of 0.1:0.95:1 and an appropriate amount of ?-butyrolactone is added and stirred for fully reaction to obtain the (GABA).sub.0.1MA.sub.0.95PbI.sub.2.1Br.sub.0.95 precursor solution. An appropriate amount of the precursor solution is filled into a carbon-materials-based counter electrode mesoscopic solar cell and dried at 60? C. and photovoltaic conversion efficiency of the solar cell is up to 9.8%.

(18) In the above examples, the amphipathic molecule is not limited to 4-aminobutyric acid and can also be other material, such as 6-aminocaproic acid, HOOCCH.sub.2CH?CHCH.sub.2NH.sub.2, 4-guanidinobutyric acid or sulfanilic acid. Generally, M is expressed by R1-RR2, R1 is selected from the group consisting of NH.sub.2, NHC(NH.sub.2)?NH and N?CHNH.sub.2, R2 is selected from the group consisting of COOH, OSiOH, O.sub.3POH and O.sub.2SOH, and R is an organic group.

(19) Besides, methylamine iodide can be replaced by chloride methylamine or bromide methylamine, PbI.sub.2 can be replaced by lead bromide, lead chloride, germanium iodide or tin iodide, and molar ratio is not limited to the above values as long as 0<z?0.5, 0<y?1 and y+z?1.

(20) The perovskite-based photoelectric functional material of the invention can be used in a solar cell as a light absorption layer, n-type or p-type materials, and can also be used in LEDs or electronic devices as a semiconductor material.

(21) While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects, and therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention.