阅读说明：本技术 一种双氨基有机化合物钝化材料及其应用 (Diamino organic compound passivation material and application thereof ) 是由 陈淑芬 马奔 钱洁 陈俊文 黄维 于 2020-06-11 设计创作，主要内容包括：本发明提出了一种双氨基有机化合物钝化材料,所述双氨基有机化合物钝化材料包括烷基链段、芳香烃或杂环化合物,所述烷基链段、芳香烃或杂环化合物上包含至少两个官能团A,所述官能团A为氨基。本发明提供的双氨基有机化合物钝化材料可以通过分子中两个氨基基团与钙钛矿中的卤素离子形成氢键,增强钙钛矿薄膜结晶度,提高载流子寿命,钝化钙钛矿缺陷。在光电器件领域有很好的应用潜力。(The invention provides a diamino organic compound passivation material which comprises an alkyl chain segment, aromatic hydrocarbon or a heterocyclic compound, wherein the alkyl chain segment, the aromatic hydrocarbon or the heterocyclic compound comprises at least two functional groups A, and the functional groups A are amino groups. The double-amino organic compound passivation material provided by the invention can form hydrogen bonds with halogen ions in perovskite through two amino groups in molecules, so that the crystallinity of the perovskite film is enhanced, the service life of a carrier is prolonged, and the defects of the perovskite are passivated. Has good application potential in the field of photoelectric devices.)

1. The diamino organic compound passivation material is characterized by comprising an alkyl chain segment, aromatic hydrocarbon or a heterocyclic compound, wherein the alkyl chain segment, the aromatic hydrocarbon or the heterocyclic compound comprises at least two functional groups A, and the functional groups A are amino groups.

2. The passivation material of claim 1, wherein the alkyl segment, the aromatic hydrocarbon or the heterocyclic compound comprises a functional group B, and the functional group B is at least one of a carboxyl group, a thiol group, a hydroxyl group, an aliphatic group, an amide group, a nitro group, an aldehyde group, an aryl group, a cyano group, and a sulfonic group.

3. The passivation material of claim 2, wherein the structural formula of the passivation material is as follows:

in the formula, R is any one of an alkyl chain segment, aromatic hydrocarbon or heterocyclic compound, and X is at least one of carboxyl, sulfydryl, hydroxyl, aliphatic group, amide, nitro, aldehyde group, aryl, cyano and sulfonic group.

4. Use of a bisamino organic compound passivation material according to any of claims 1 to 3, characterized in that: the diamino organic compound passivation material is directly used as an additive to prepare the perovskite thin film.

5. The application of the bisamino organic compound passivation material as claimed in claim 4, wherein the perovskite thin film is prepared by a process comprising the following steps:

(1) dissolving a diamino organic compound passivation material, a metal source compound and an organic/inorganic source halide in a mixed polar solvent according to different stoichiometric ratios, and uniformly stirring to prepare a perovskite precursor solution;

(2) spin-coating the perovskite precursor solution on an ITO substrate deposited with a hole transmission layer, then dripping an anti-solvent, and then annealing to form a smooth, compact and hole-free perovskite thin film.

6. Use of a bisamino organic compound passivation material according to any of claims 1 to 3, characterized in that: the bisamino organic compound passivation material is directly used for interface treatment to prepare the perovskite thin film.

7. The application of the bisamino organic compound passivation material as claimed in claim 6, wherein the perovskite thin film is prepared by a process comprising the following steps:

(1) dissolving a metal source compound and organic/inorganic source halide in a mixed polar solvent according to different stoichiometric ratios, and uniformly stirring to prepare a perovskite precursor solution;

(2) spin-coating a perovskite precursor solution on a substrate, then dropwise adding an anti-solvent, and then annealing to form a flat, compact and pore-free perovskite thin film;

(3) and dissolving the bisamino organic compound passivation material in a polar solvent, and spin-coating the bisamino organic compound passivation material between the perovskite thin film and other functional layers.

8. Use of a bis-amino organic compound passivation material according to claim 5 or 7, characterized in that: the metal source compound is at least one of a lead-based source compound, a tin-based source compound, a copper-based source compound and a germanium-based source compound, the lead-based source compound is lead halide, the tin-based source compound is stannous halide, the copper-based source compound is copper halide, and the germanium-based source compound is germanium halide; the organic/inorganic source halide is at least one of formamidine hydrohalide, methylamine hydrohalide and cesium halide.

9. Use of a bis-amino organic compound passivation material according to claim 8, characterized in that: the mixed polar solvent consists of DMF and DMSO, and the volume ratio of the DMF to the DMSO is 4: 1; the molar ratio of the metal source compound to the organic/inorganic source halide is 1:1, and the addition amount of the diamino organic compound passivation material is x mol%, wherein x is more than or equal to 0 and less than or equal to 20.

10. Use of a bis-amino organic compound passivation material according to claim 9, characterized in that: the perovskite thin film may be applied to perovskite optoelectronic devices including solar cells, perovskite luminescence, photodetectors and lasers.

Technical Field

The invention relates to a diamino organic compound passivation material and application of the material to passivation of perovskite, belonging to the technical field of photoelectric materials and devices.

Background

Perovskite materials are a class having ABX₃Crystal structures of the general structural formula, wherein A generally refers to some organic cations (e.g., methylamine cation CH)₃NH₃ ⁺Formamidine cation NH ═ CHNH₃ ⁺Or cesium ions Cs⁺) Occupies eight vertices of the cube; b refers to a metal ion (e.g., Pb)²⁺，Sn²⁺，Cu²⁺，Ge²⁺) At the body center of the cube; x represents a halogen ion (e.g. I)^-，Br^-，Cl^-) Occupying the face center of the hexahedron.

At present, perovskite materials are widely applied to the fields of perovskite solar cells, perovskite luminescence, photodetectors, lasers and the like. However, perovskite thin films prepared based on the prior art generally have a large number of defects, the defects are mainly located on the crystal surface and grain boundaries, and the improvement of the performance and stability of the optoelectronic device is extremely unfavorable. The passivation of surface dangling bonds and grain boundary defects of perovskite materials has become an important means for inhibiting the non-radiative recombination of carriers in perovskite film layers.

So far, it has been reported that amino groups can form hydrogen bonds with halogen ions in perovskite, thereby enhancing the crystallinity of perovskite thin film, prolonging the service life of carriers, and passivating perovskite defects. In addition, functional groups like carboxyl and the like interact with charged defects of the perovskite film layer, and the perovskite film layer is well regulated and controlled. For example, work has continued to demonstrate that materials with diamino functionality, such as ethylenediamine, propylenediamine, trimethylenediamine, etc., can passivate perovskite defects and improve film quality.

Disclosure of Invention

The invention aims to solve the technical problems of a great number of defects of perovskite, poor device efficiency and stability performance and the like in the prior art, and provides a bisamino organic compound passivation material and application thereof.

The invention provides a diamino organic compound passivation material which comprises an alkyl chain segment, aromatic hydrocarbon or heterocyclic compound, wherein the alkyl chain segment, the aromatic hydrocarbon or the heterocyclic compound comprises at least two functional groups A, and the functional groups A are amino groups.

The diamino organic compound passivation material provided by the invention comprises a functional group B on the alkyl chain segment, the aromatic hydrocarbon or the heterocyclic compound, wherein the functional group B is at least one of carboxyl, sulfydryl, hydroxyl, aliphatic group, amide, nitro, aldehyde group, aryl, cyano and sulfonic group.

The double-amino organic compound passivation material provided by the invention can form hydrogen bonds with halogen ions in perovskite through two amino groups in molecules, thereby not only enhancing the crystallinity of the perovskite thin film and prolonging the service life of a carrier, but also passivating the charged defects of the perovskite. In addition, the functional group B also plays a good role in regulating and controlling the perovskite thin film. The perovskite prepared by the bisamino organic compound passivation material has wide application in the field of photoelectric devices such as solar cells, perovskite luminescence, photodetectors, lasers and the like.

As a further technical scheme of the invention, the general structural formula of the diamino organic compound passivation material is shown as follows:

wherein R is any one of an alkyl segment, an aromatic hydrocarbon or a heterocyclic compound, and when R is an alkyl segment, then R ═ (CH)₂)_nN is more than or equal to 1 and less than or equal to 6, and n is an integer; x is at least one of carboxyl, sulfydryl, hydroxyl, aliphatic group, amide, nitro, aldehyde group, aryl, cyano and sulfonic group.

The diamino organic compound passivation material provided by the invention is directly used as an additive to prepare a perovskite thin film. The preparation process comprises the following steps:

(1) dissolving a diamino organic compound passivation material, a metal source compound and an organic/inorganic source halide in a mixed polar solvent according to different stoichiometric ratios, and uniformly stirring to prepare a perovskite precursor solution;

(2) spin-coating the perovskite precursor solution on an ITO substrate deposited with a hole transmission layer, then dripping an anti-solvent, and then annealing to form a smooth, compact and hole-free perovskite thin film.

The diamino organic compound passivation material provided by the invention is directly used for interface treatment to prepare a perovskite thin film. The preparation process comprises the following steps:

(1) dissolving a metal source compound and organic/inorganic source halide in a mixed polar solvent according to different stoichiometric ratios, and uniformly stirring to prepare a perovskite precursor solution;

(2) spin-coating a perovskite precursor solution on a substrate, then dropwise adding an anti-solvent, and then annealing to form a flat, compact and pore-free perovskite thin film;

(3) and dissolving the bisamino organic compound passivation material in a polar solvent, and spin-coating the bisamino organic compound passivation material between the perovskite thin film and other functional layers.

The invention provides a double-amino organic compound passivation material containing two amino groups and other functional groups, which is introduced into a perovskite precursor solution or directly coated between a perovskite layer and other functional layers in a spin mode, so that the crystallization process of perovskite can be well regulated, the defects on the surface and grain boundaries of a film can be effectively passivated, and a flat and compact perovskite film can be obtained.

Further, the metal source compound is at least one of a lead-based source compound, a tin-based source compound, a copper-based source compound and a germanium-based source compound, the lead-based source compound is a lead halide, the tin-based source compound is a stannous halide, the copper-based source compound is a copper halide, and the germanium-based source compound is a germanium halide; the organic/inorganic source halide is at least one of formamidine hydrohalide, methylamine hydrohalide and cesium halide.

Further, the mixed polar solvent consists of DMF and DMSO, and the volume ratio of the DMF to the DMSO is 4: 1; the polar solvent is DMF or DMSO. The molar ratio of the metal source compound to the organic/inorganic source halide is 1:1, and the addition amount of the diamino organic compound passivation material is x mol%, wherein x is more than or equal to 0 and less than or equal to 20. The anti-solvent is chlorobenzene.

The perovskite thin film prepared by the method has high quality, and can be applied to perovskite photoelectric devices, wherein the perovskite photoelectric devices comprise solar cells, perovskite luminescence, photoelectric detectors, lasers and the like.

Compared with the prior art, the invention adopting the technical scheme has the following technical effects:

(1) the double-amino organic compound passivation material provided by the invention can well regulate and control the crystallization process of the perovskite film, and the perovskite film with better crystallinity and larger grain size is prepared;

(2) the bisamino organic compound provided by the invention can passivate defects on the surface and the grain boundary of the perovskite and improve the quality of a film layer;

(3) the double-amino organic compound provided by the invention has diversified passivation modes on perovskite, is simple in preparation process and is easy to apply to industrial production;

(4) the perovskite photoelectric device provided by the invention has simple preparation process;

(5) the perovskite device passivated by the bisamino organic compound provided by the invention has excellent performance, and the application potential of the bisamino organic compound in the field of photoelectric devices such as perovskite solar cells, perovskite luminescence, photodetectors, lasers and the like is shown.

In a word, the double-amino organic compound passivation material provided by the invention can form hydrogen bonds with halogen ions in perovskite through two amino groups in molecules, so that the crystallinity of the perovskite thin film is enhanced, the carrier life is prolonged, and the perovskite defects are passivated. Has good application potential in the field of photoelectric devices.

Drawings

The invention is further described below with reference to the figures and examples.

FIG. 1 is FASnI₃、HDADI-doped FASnI₃XRD patterns of perovskite thin films;

FIG. 2 is FASnI₃HDADI doped FASnI₃Photoluminescence spectra of the perovskite thin film;

FIG. 3 is FASnI₃HDADI doped FASnI₃Ultraviolet-visible absorption spectrum of the perovskite thin film;

FIG. 4 is FASnI₃HDADI doped FASnI₃SEM images of perovskite thin films;

FIG. 5 is a device structure diagram of the present invention in the field of optoelectronic devices, exemplified by perovskite solar cells;

FIG. 6 is FASnI₃HDADI doped FASnI₃A perovskite solar cell J-V characteristic curve;

FIG. 7 is FASnI₃HDADI doped FASnI₃The efficiency of the perovskite solar cell in the nitrogen-unencapsulated condition tracks the curve.

Detailed Description

The technical scheme of the invention is further explained in detail by combining the attached drawings: the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection authority of the present invention is not limited to the following embodiments.