CN111690978B - Layered organic-inorganic hybrid perovskite crystal and synthesis method thereof - Google Patents

Layered organic-inorganic hybrid perovskite crystal and synthesis method thereof Download PDF

Info

Publication number
CN111690978B
CN111690978B CN202010534687.2A CN202010534687A CN111690978B CN 111690978 B CN111690978 B CN 111690978B CN 202010534687 A CN202010534687 A CN 202010534687A CN 111690978 B CN111690978 B CN 111690978B
Authority
CN
China
Prior art keywords
inorganic hybrid
hybrid perovskite
perovskite crystal
layered organic
crystal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010534687.2A
Other languages
Chinese (zh)
Other versions
CN111690978A (en
Inventor
马德伟
蓝玉国
代宁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN202010534687.2A priority Critical patent/CN111690978B/en
Publication of CN111690978A publication Critical patent/CN111690978A/en
Application granted granted Critical
Publication of CN111690978B publication Critical patent/CN111690978B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
    • C30B7/06—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using non-aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/54—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Luminescent Compositions (AREA)

Abstract

A preparation method of a layered organic-inorganic hybrid perovskite crystal comprises the following steps: dissolving cuprous iodide and phenethyl ammonia iodine in acetonitrile, then dripping oleic acid, and uniformly mixing to obtain a composition C6H5CH2CH2NH3CuI2Filtering the precursor solution, and freely evaporating filtrate in air at room temperature to dryness to obtain the layered organic-inorganic hybrid perovskite crystal; the preparation method has the advantages of short preparation period, simple operation, low requirement on environment, and good application prospect of the obtained organic-inorganic hybrid perovskite crystal in the field of photoelectric devices such as LEDs, lasers and the like, and the simple and cheap preparation method has great potential for the commercial application of the crystal, and the crystal growth time can be adjusted by the volume ratio of acetonitrile to oleic acid.

Description

Layered organic-inorganic hybrid perovskite crystal and synthesis method thereof
Technical Field
The invention relates to a novel lead-free layered organic-inorganic hybrid perovskite crystal and a synthesis method thereof, wherein the layered organic-inorganic hybrid perovskite crystal can be applied as a luminescent material.
Background
The organic-inorganic perovskite material has excellent performance and strong competitiveness in the aspects of photoelectric devices such as photovoltaic devices, light-emitting diodes, photoelectric detectors and the like. The perovskite material has excellent film forming ability. Heretofore, there have been many methods including spin coating, vacuum vapor deposition, two-step dipping method, etc. for producing a perovskite polycrystalline thin film. Single crystal materials are generally considered to have a very low defect density and a long carrier transport distance, thereby having more excellent photoelectric properties than polycrystalline thin films. However, due to the significantly different physicochemical properties of the organic and inorganic parts, the synthesis of organic-inorganic single crystal materials often faces enormous challenges.
Compared with the high-temperature melt cooling method commonly used for preparing single crystal materials in the semiconductor industry, the organic and inorganic perovskite can be chemically decomposed at high temperature. Therefore, organic-inorganic perovskite crystal synthesis generally employs a crystal growth technique in solution. At present, the main methods for synthesizing the organic-inorganic perovskite single crystal comprise a seed crystal induction growth method, a supersaturated solution cooling method, an anti-solvent gas phase auxiliary crystallization method, a solvothermal method and the like. Moreover, the organic and inorganic perovskite materials reported at present are mostly lead-containing perovskite crystals, and lead toxicity is a key factor for restricting the implementation and application of the perovskite materials.
Disclosure of Invention
The invention aims to provide a novel lead-free layered organic-inorganic hybrid perovskite crystal which can be used as a luminescent material and a synthesis method thereof.
The technical scheme of the invention is as follows:
a layered organic-inorganic hybrid perovskite crystal is prepared by the following method:
mixing cuprous iodide (CuI) and phenethylamine iodine (C)6H5CH2CH2NH3I) Dissolving in acetonitrile, dripping oleic acid, and mixing to obtain composition C6H5CH2CH2NH3CuI2Filtering the precursor solution (to remove insoluble part of residues), and freely evaporating the filtrate in the air at room temperature (20-30 ℃) for 3-7 days to obtain the layered organic-inorganic hybrid perovskite crystal;
the ratio of the cuprous iodide to the phenylethylamine iodine is 1: 1;
the volume ratio of the acetonitrile to the oleic acid is 2-4: 1;
in the precursor solution, C6H5CH2CH2NH3CuI2The concentration of (b) is 0.05-0.2 mol/L.
The chemical composition of the layered organic-inorganic hybrid perovskite crystal prepared by the invention is C6H5CH2CH2NH3CuI2The crystal has good luminescence property.
Compared with the crystal growth method in the prior art, the method has short preparation period, and the crystal growth time can be adjusted by the volume ratio of the solvents acetonitrile and oleic acid. The method disclosed by the invention is simple to operate, has low requirements on environment, and the obtained organic-inorganic hybrid perovskite crystal has a good application prospect in the field of photoelectric devices such as LEDs, lasers and the like, and the simple and cheap preparation method has great potential for the commercial application of the crystal.
Drawings
FIG. 1 preparation of C of example 16H5CH2CH2NH3CuI2Optical micrograph of the crystal.
FIG. 2 preparation C of example 16H5CH2CH2NH3CuI2XRD pattern of the crystal.
FIG. 3 preparation of C of example 16H5CH2CH2NH3CuI2PL spectrum of the crystal.
Detailed Description
The invention will be further illustrated and described with reference to specific embodiments, but the scope of the invention is not limited thereto.
Example 1:
mixing CuI (0.114g, 0.6mmol) and C6H5CH2CH2NH3Adding I (0.15g, 0.6mmol) into 4ml acetonitrile, after completely dissolving, dropwise adding 2ml oleic acid to fully mix and vibrate to obtain composition C6H5CH2CH2NH3CuI2The precursor solution of (1). Filtering the precursor solution, putting the filtered precursor solution into a clean 20ml sample bottle, and placing the sample bottle at room temperature to allow the sample solution to be freely evaporated to dryness to obtain the layered organic-inorganic hybrid perovskite C6H5CH2CH2NH3CuI2And (4) crystals.
Example 2:
mixing CuI (0.114g, 0.6mmol) and C6H5CH2CH2NH3I (0.15g, 0.6mmol) was added to 4ml acetonitrile and after complete dissolution 1.5ml oleic acid was added dropwiseMixing them fully and oscillating to obtain composition C6H5CH2CH2NH3CuI2The precursor solution of (1). Filtering the precursor solution, putting the filtered precursor solution into a clean 20ml sample bottle, and placing the sample bottle at room temperature to allow the sample solution to be freely evaporated to dryness to obtain the layered organic-inorganic hybrid perovskite C6H5CH2CH2NH3CuI2And (4) crystals.
Example 3:
mixing CuI (0.114g, 0.6mmol) and C6H5CH2CH2NH3Adding I (0.15g, 0.6mmol) into 4ml acetonitrile, after completely dissolving, dropwise adding 1ml oleic acid to fully mix and vibrate to obtain composition C6H5CH2CH2NH3CuI2Filtering the precursor solution, putting the filtered precursor solution into a clean 20ml sample bottle, and placing the sample bottle at room temperature to allow the sample solution to be freely evaporated to dryness to obtain the layered organic-inorganic hybrid perovskite C6H5CH2CH2NH3CuI2And (4) crystals.
Compared with the lead-containing halide perovskite widely reported at present, the copper-based halide perovskite disclosed by the invention has the characteristics of no toxicity, greenness and environmental friendliness, and has the important application potential of substituting the lead-based perovskite on photoelectric devices such as solar cells, LEDs and the like due to the excellent luminescence property.

Claims (4)

1. A layered organic-inorganic hybrid perovskite crystal is characterized by being prepared by the following method:
dissolving cuprous iodide and phenethylamine iodine in acetonitrile, then dropwise adding oleic acid, and uniformly mixing to obtain a composition C6H5CH2CH2NH3CuI2Filtering the precursor solution, and freely evaporating filtrate in air at room temperature to dryness to obtain the layered organic-inorganic hybrid perovskite crystal;
the ratio of the cuprous iodide to the phenylethylamine iodine is 1: 1.
2. the layered organic-inorganic hybrid perovskite crystal according to claim 1, wherein the volume ratio of acetonitrile to oleic acid is 2 to 4: 1.
3. the layered organic-inorganic hybrid perovskite crystal according to claim 1, wherein in the precursor solution, C is6H5CH2CH2NH3CuI2The concentration of (b) is 0.05-0.2 mol/L.
4. Use of the layered organic-inorganic hybrid perovskite crystal as defined in claim 1 as a light-emitting material in an optoelectronic device.
CN202010534687.2A 2020-06-12 2020-06-12 Layered organic-inorganic hybrid perovskite crystal and synthesis method thereof Active CN111690978B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010534687.2A CN111690978B (en) 2020-06-12 2020-06-12 Layered organic-inorganic hybrid perovskite crystal and synthesis method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010534687.2A CN111690978B (en) 2020-06-12 2020-06-12 Layered organic-inorganic hybrid perovskite crystal and synthesis method thereof

Publications (2)

Publication Number Publication Date
CN111690978A CN111690978A (en) 2020-09-22
CN111690978B true CN111690978B (en) 2021-07-27

Family

ID=72480730

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010534687.2A Active CN111690978B (en) 2020-06-12 2020-06-12 Layered organic-inorganic hybrid perovskite crystal and synthesis method thereof

Country Status (1)

Country Link
CN (1) CN111690978B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105671640A (en) * 2015-12-29 2016-06-15 东南大学 Layered large-size hybridized perovskite microcrystal material and preparation method thereof
CN105926040A (en) * 2016-06-24 2016-09-07 哈尔滨工业大学 Preparation method of organic-inorganic hybrid perovskite structure crystal using diisopropylamine halide salt as precursor material
CN107502355A (en) * 2017-09-22 2017-12-22 苏州轻光材料科技有限公司 A kind of perovskite structure of the height adjustability high and photochromic with luminous efficiency
CN109853031A (en) * 2019-02-27 2019-06-07 中南大学 A kind of high quality two-dimensional layer lead iodide perovskite monocrystal material and preparation method thereof
CN110158153A (en) * 2019-05-13 2019-08-23 浙江工业大学 A kind of preparation method of needle-shaped two-dimentional organic-inorganic perovskite fluoride micro-nano material
CN110552066A (en) * 2019-09-25 2019-12-10 浙江工业大学 Synthesis method of tetragonal flat plate-shaped (C 6 H 5 CH 2 CH 2 NH 3) 2 MnCl 4 micro-nano single crystal
CN110854274A (en) * 2019-11-22 2020-02-28 中南大学 Regulating and controlling method for perovskite nucleation process and preparation method for perovskite thin film based solar cell

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105671640A (en) * 2015-12-29 2016-06-15 东南大学 Layered large-size hybridized perovskite microcrystal material and preparation method thereof
CN105926040A (en) * 2016-06-24 2016-09-07 哈尔滨工业大学 Preparation method of organic-inorganic hybrid perovskite structure crystal using diisopropylamine halide salt as precursor material
CN107502355A (en) * 2017-09-22 2017-12-22 苏州轻光材料科技有限公司 A kind of perovskite structure of the height adjustability high and photochromic with luminous efficiency
CN109853031A (en) * 2019-02-27 2019-06-07 中南大学 A kind of high quality two-dimensional layer lead iodide perovskite monocrystal material and preparation method thereof
CN110158153A (en) * 2019-05-13 2019-08-23 浙江工业大学 A kind of preparation method of needle-shaped two-dimentional organic-inorganic perovskite fluoride micro-nano material
CN110552066A (en) * 2019-09-25 2019-12-10 浙江工业大学 Synthesis method of tetragonal flat plate-shaped (C 6 H 5 CH 2 CH 2 NH 3) 2 MnCl 4 micro-nano single crystal
CN110854274A (en) * 2019-11-22 2020-02-28 中南大学 Regulating and controlling method for perovskite nucleation process and preparation method for perovskite thin film based solar cell

Also Published As

Publication number Publication date
CN111690978A (en) 2020-09-22

Similar Documents

Publication Publication Date Title
Nenon et al. Structural and chemical evolution of methylammonium lead halide perovskites during thermal processing from solution
Wang et al. Isothermally crystallized perovskites at room-temperature
US8057850B2 (en) Formation of copper-indium-selenide and/or copper-indium-gallium-selenide films from indium selenide and copper selenide precursors
EP2101931B1 (en) Precursors for formation of copper selenide, indium selenide, copper indium diselenide, and/or copper indium gallium diselenide films
US9196482B2 (en) Solution-based synthesis of CsSnI3
US20230070055A1 (en) Precursor solution for copper-zinc-tin-sulfur thin film solar cell, preparation method therefor, and use thereof
US10883193B2 (en) Method for preparing perovskite crystal
CN111129319B (en) Cs (cell lines) n FA 1-n PbX 3 Preparation method of perovskite film
JP2022542724A (en) Composite light-emitting material, its production method and its use
CN110776906B (en) Perovskite thin film with stable photoluminescence efficiency and preparation method thereof
WO2019031991A1 (en) Method for producing a film of light-absorbing material with a perovskite-like structure
CN103613114A (en) Liquid-phase preparation method of cuprous sulfide film
WO2013185866A1 (en) Precursor solution for forming a semiconductor thin film on the basis of cis, cigs or czts
CN111690978B (en) Layered organic-inorganic hybrid perovskite crystal and synthesis method thereof
US20130323878A1 (en) Liquid precursor inks for deposition of in-se, ga-se and in-ga-se
US20200203633A1 (en) Perovskite Film, Method for Producing the Same, Light-emitting device and Solar Cell
Ndione et al. Monitoring the stability of organometallic perovskite thin films
CN110054212B (en) Compound NH4GaS2And preparation method and application thereof
CN114649482A (en) Preparation method of trans-solar cell based on seed crystal induced growth of perovskite film
CN115161012A (en) Perovskite material, thin film, solar cell device and preparation method thereof
CN1400331A (en) Method for growing ZnO film by solid source chemical gas-phase deposition
KR101623923B1 (en) Method for fabricating buffer layer of thin film type solar cell
KR101851842B1 (en) Film, manufacturing metohd of the film and light emitting diode comprising thereof
CN1199949C (en) High-purity 8-hydroxyquinoline aluminium group compound, preparation method and use thereof
CN111170649A (en) Method for preparing cesium-based all-inorganic perovskite material through low-temperature reaction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant