CN-121976297-A - Zero-dimensional perovskite single crystal, zero-dimensional/three-dimensional perovskite thin film, perovskite battery and preparation method

Abstract

The invention discloses a zero-dimensional perovskite single crystal, a zero-dimensional/three-dimensional perovskite film, a perovskite battery and a preparation method, wherein the chemical general formula of the zero-dimensional perovskite single crystal is (C 9 H 17 N 3 )PbI 5 ×2H 2 O), the zero-dimensional perovskite single crystal comprises basic structural units formed by dimer anion clusters [ Pb 2 I 10 ] 6‑ ], the basic structural units are separated in three-dimensional space through [ C 9 H 17 N 3 ] 3+ ] and water molecules to form a zero-dimensional structure, the single crystal structure physically blocks the path of ion migration, and the hydrophobic benzene ring structure of [ C 9 H 17 N 3 ] 3+ ] endows the material with intrinsic high environmental stability, and provides a brand new basic material for preparing high-efficiency stable photoelectric devices.

Inventors

• LIU YANG
• WANG HAIQIAO
• FU JIANFEI

Assignees

• 浙大宁波理工学院

Dates

Publication Date

20260505

Application Date

20260128

Claims (10)

1. 1. The zero-dimensional perovskite single crystal is characterized by having a chemical formula of (C 9 H 17 N 3 )PbI 5 ×2H 2 O), and comprises basic structural units consisting of dimer anion clusters [ Pb 2 I 10 ] 6- ], wherein the basic structural units are separated in three-dimensional space through [ C 9 H 17 N 3 ] 3+ ] and water molecules to form a zero-dimensional structure.
2. 2. The zero-dimensional perovskite single crystal according to claim 1, wherein the zero-dimensional perovskite single crystal belongs to a triclinic system and the space group is P-1.
3. 3. The zero-dimensional perovskite single crystal according to claim 2, wherein the unit cell parameters of the zero-dimensional perovskite single crystal are a= 10.8731 (7) a, b= 11.1762 (5) a, c= 11.3114 (5) a, α= 60.965 (4) °, β= 69.390 (5) °, γ= 70.036 (5) °.
4. 4. The zero-dimensional perovskite single crystal according to claim 1, wherein the X-ray diffraction spectrum of the zero-dimensional perovskite single crystal has characteristic peaks at the following 2Θ angles of 8.5 °,12.4 °,17.1 °,22.9 °,27.3 °, with an error range of ± 0.2 °.
5. 5. A method for producing a zero-dimensional perovskite single crystal as claimed in any one of claims 1 to 4, comprising the steps of: Uniformly mixing lead oxide, hydroiodic acid and hypophosphorous acid to form a mixed solution; Adding 1,3, 5-benzene trimethylamine into the mixed solution, and stirring for reaction at 180-240 ℃; and cooling the reacted system to room temperature, and separating out crystals to obtain the zero-dimensional perovskite single crystal.
6. 6. The method for producing a single crystal of zero-dimensional perovskite according to claim 5, wherein the molar ratio of lead oxide to 1,3, 5-benzenetrimethylamine is 1:1.
7. 7. A zero-dimensional/three-dimensional perovskite thin film, characterized in that the thin film is a composite phase thin film formed by film formation and heat treatment of a three-dimensional perovskite precursor solution, wherein the three-dimensional perovskite precursor solution comprises the zero-dimensional perovskite single crystal according to any one of claims 1-4.
8. 8. The zero-dimensional/three-dimensional perovskite thin film according to claim 7, wherein the concentration of the zero-dimensional perovskite single crystal in the three-dimensional perovskite precursor solution is 5.0-15.0mg/mL.
9. 9. The zero-dimensional/three-dimensional perovskite thin film according to claim 8, wherein the solvent of the three-dimensional perovskite precursor solution comprises N, N-dimethylformamide and dimethylsulfoxide, and the solute comprises formamidine iodine, lead iodide, methyl ammonium bromide, lead bromide, methyl ammonium chloride and the zero-dimensional perovskite single crystal.
10. 10. A perovskite solar cell, which is characterized by comprising a transparent conductive substrate, a hole transmission layer, a perovskite light absorption layer, an electron transmission layer, a barrier layer and a metal electrode layer which are sequentially stacked, wherein the perovskite light absorption layer is made of the zero-dimensional/three-dimensional perovskite film according to any one of claims 7-9.

Description

Zero-dimensional perovskite single crystal, zero-dimensional/three-dimensional perovskite thin film, perovskite battery and preparation method Technical Field The invention relates to the technical field of solar cells, in particular to a zero-dimensional perovskite single crystal, a zero-dimensional/three-dimensional perovskite thin film, a perovskite cell and a preparation method. Background Perovskite solar cells have made breakthrough progress in photoelectric conversion efficiency in recent years as outstanding representatives of the next generation of photovoltaic technology, and have demonstrated great commercial application potential. The core bottleneck which restricts the practical application and large-scale industrialization from the laboratory is the long-term operation stability of the device. Traditional three-dimensional perovskite materials, such as MAPbI 3 and FAPbI 3, are extremely sensitive to environmental moisture, oxygen, light, and thermal stresses. More importantly, a large number of defect states exist on the surface and the grain boundary of the three-dimensional perovskite film, and the defects not only serve as non-radiative recombination centers and severely restrict further improvement of the efficiency of the battery, but also provide a rapid channel for invasion of moisture and oxygen, so that degradation of materials and degradation of performances are aggravated. In order to solve the stability problem, the scientific research world directs the eyes to low-dimensional perovskite materials, in particular to zero-dimensional perovskite with unique structure. The zero-dimensional perovskite is essentially different in crystal structure from a three-dimensional perovskite in that its structure is composed of completely isolated [ PbX 6]4- octahedral anion clusters, which are completely separated in three dimensions by larger, structurally more stable organic cations (spacer molecules) like individual "islands". The unique island-shaped structure brings two major core advantages that firstly, active ions such as halogen ions are limited in isolated octahedral units, long-range migration paths of the active ions are physically blocked, so that ion migration phenomenon causing performance degradation can be fundamentally and effectively inhibited, and secondly, the selected large-size organic spacing cations generally have good hydrophobicity, can form a natural molecular barrier around perovskite grains, remarkably block permeation of water molecules and improve intrinsic environmental stability of materials. Although zero-dimensional perovskite is one of ideal material systems for solving the problem of three-dimensional perovskite stability in theory, practical research and application in the photovoltaic field is still in the primary stage. One significant limitation is the relatively limited variety of zero-dimensional perovskite currently known and successfully synthesized for use in photovoltaic devices, and the need for a rich library of materials. The existing researches focus on a few classical spacer molecules, and the obtained zero-dimensional perovskite has the defects of energy band structure, solubility, compatibility with three-dimensional perovskite and the like. Therefore, developing new, structurally diverse, organically-spaced cations to expand the material system of the zero-dimensional perovskite and to dig its synergistic potential in terms of improving the efficiency and stability of perovskite solar cells has become a current critical and challenging research direction. Furthermore, there are different technical paths how the advantages of the zero-dimensional perovskite can be effectively introduced into optoelectronic devices. In the prior art, a common thinking is to spin-coat a spacer molecule solution on the surface of a three-dimensional perovskite which is formed into a film by adopting a post-treatment mode, so that the spacer molecule solution reacts with PbI 2 remained on the surface to form a low-dimensional covering layer (surface passivation). However, this method acts mainly on the surface interface of the thin film, and has limited effects of improving the crystal quality inside the bulk phase of the three-dimensional perovskite light-absorbing layer and inhibiting bulk ion migration, and it is difficult to achieve deep optimization of device performance. Disclosure of Invention The invention aims to solve the technical problems that the existing perovskite material has poor intrinsic stability and many bulk defects, so that the efficiency of a solar cell is difficult to further improve, and the long-term stability is insufficient. In order to solve the above problems, a first aspect of the present invention provides a zero-dimensional perovskite single crystal having a chemical formula (C 9H17N3)PbI5×2H2 O), the zero-dimensional perovskite single crystal comprising basic structural units composed of dimer anion clusters [ Pb 2I10]6-, the b