CN106065494B - A kind of synthetic method of morphology controllable hybrid inorganic-organic bismuthino crystal - Google Patents

A kind of synthetic method of morphology controllable hybrid inorganic-organic bismuthino crystal Download PDF

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CN106065494B
CN106065494B CN201610397867.4A CN201610397867A CN106065494B CN 106065494 B CN106065494 B CN 106065494B CN 201610397867 A CN201610397867 A CN 201610397867A CN 106065494 B CN106065494 B CN 106065494B
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organic
crystal
temperature
bismuthino
absolute ethyl
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CN106065494A (en
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王传义
赵赫
李英宣
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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    • 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
    • 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
    • C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention relates to a kind of synthetic methods of morphology controllable organic inorganic hybridization bismuthino crystal, this method forms the principle of crystalline material based on solvent thermal reaction, it is synthesized by bismuthino material solution, prepared by solvent heat crystal, product washing and vacuum drying step are completed, the method of the invention passes through the type of control solvent, the crystal of controlledly synthesis different-shape.Solvothermal preparation method provided by the invention has many advantages, such as easy to operate, mild condition, simple for process；Influence of the solvent to organic-inorganic hybrid material crystallinity and growth mechanism can be studied according to the present invention, theoretical foundation is provided to design and researching and developing novel organic-inorganic hybrid material.

Description

A kind of synthetic method of morphology controllable hybrid inorganic-organic bismuthino crystal
Technical field
The invention belongs to hybrid inorganic-organic materials preparing technical fields, and in particular to nontoxic, stable bismuthino material Synthetic method.
Background technology
With the high speed development of global economy and the rapid growth of population, the demand to the energy is growing day by day, and has found out The quantity of fossil energy is limited.Solar energy is the most abundant in the world energy, and converting solar energy into directly to use The energy be a kind of important scientific method of alleviating energy crisis.Perovskite solar cell with its high energy conversion efficiency and Low production cost is fast-developing in solar cell market.But common perovskite solar cell active layer --- methylamine Lead iodide and its homologous series substance the shortcomings of there are unstability and the toxicity of lead, constrain the quotient of perovskite solar cell Industry step.Therefore, it is particularly important as solar energy active layer that hybrid inorganic-organic materials that are nontoxic, stablizing are developed.Meanwhile The crystallinity and pattern of hybrid inorganic-organic materials are most important to the efficiency of solar cell, and the selection of solvent and its property There are prodigious correlations for the crystallinity and pattern of confrontation hybrid inorganic-organic materials.Therefore, research solvent is to organic and inorganic The influence of hybrid material crystallinity and pattern can provide theoretical foundation to design and researching and developing novel organic-inorganic hybrid material.
However, that has reported changes grinding for hybrid inorganic-organic materials crystallinity and pattern by using different solvents Study carefully and be limited only in solar cell device, and rarely have and individually study solvent to solar energy active component --- organic and inorganic is miscellaneous Change the influence of material crystals pattern.The invention can provide theoretical foundation to design and researching and developing novel organic-inorganic hybrid material.
Invention content
The object of the present invention is to provide a kind of synthetic method of morphology controllable hybrid inorganic-organic bismuthino crystal, the party Method forms the principle of crystalline material based on solvent thermal reaction, is synthesized by bismuthino material solution, prepared by solvent heat crystal, product washing And vacuum drying step is completed, the method for the invention can pass through the type of control solvent, the crystalline substance of controlledly synthesis different-shape Body.Solvothermal preparation method provided by the invention has many advantages, such as easy to operate, mild condition, simple for process；It can according to the present invention Influence of the solvent to hybrid inorganic-organic materials crystallinity and growth mechanism is studied, it is miscellaneous to design and researching and developing novel organic-inorganic Change material and theoretical foundation is provided.
A kind of synthetic method of morphology controllable hybrid inorganic-organic bismuthino crystal of the present invention, this method is taken molten The hot method of agent prepares the hybrid inorganic-organic bismuthino crystal of different-shape, following step is pressed in concrete operations by the way that different solvents are added It is rapid to carry out：
A. by 0.103g Bi2S3It is dissolved in the hydroiodic acid that 2mL mass fractions are 57%, uses 0.45 μm of membrane filtration；
B. by 0.382g CH3NH3I is dissolved in 12mL absolute ethyl alcohols, is at the uniform velocity stirred the solution that lower a dropping step a is obtained, is obtained To mixed solution；
Or by 0.382g CH3NH3I is dissolved in 12mL absolute ethyl alcohols, adds the n,N-Dimethylformamide or pyrrole of 800 μ L Pyridine at the uniform velocity stirs the solution that lower a dropping step a is obtained, obtains mixed solution；
C. the obtained mixed solutions of step b are moved into the autoclave of 50mL, 140 DEG C of temperature, heating rate 1 DEG C/min, heat preservation for 24 hours, is naturally cooling to room temperature, then wash 3 times with absolute ethyl alcohol, and temperature 60 C is dried in vacuo to get to target The hybrid inorganic-organic bismuthino crystal of product hexagon.
Description of the drawings
Fig. 1 is hexagon hybrid inorganic-organic bismuthino crystal optics microscope photo prepared by the present invention.
Fig. 2 is rodlike hybrid inorganic-organic bismuthino crystal optics microscope photo prepared by the present invention.
Fig. 3 is prismatic hybrid inorganic-organic bismuthino crystal optics microscope photo prepared by the present invention.
Specific implementation mode
Under premised on technical solution of the present invention, detailed embodiment and specific operating process, but this hair are given It is bright to be not limited only to following embodiments：
Embodiment 1
A. by 0.103g Bi2S3It is dissolved in the hydroiodic acid that 2mL mass fractions are 57%, uses 0.45 μm of membrane filtration；
B. by 0.382g CH3NH3I is dissolved in 12mL absolute ethyl alcohols, and the solution that step a is obtained is added dropwise under at the uniform velocity stirring, Obtain mixed solution；
C. the obtained solution of step b is moved into the autoclave of 50mL, 140 DEG C of temperature, 1 DEG C of heating rate/ Min, heat preservation for 24 hours, are naturally cooling to room temperature, then washed 3 times with absolute ethyl alcohol, and temperature 60 C is dried in vacuo to get target product The hybrid inorganic-organic bismuthino crystal (Fig. 1) of hexagon.
Embodiment 2
A. by 0.103g Bi2S3It is dissolved in the hydroiodic acid that 2mL mass fractions are 57%, uses 0.45 μm of membrane filtration；
B. by 0.382g CH3NH3I is dissolved in 12mL absolute ethyl alcohols, adds 800 μ L n,N-Dimethylformamide, at the uniform velocity It is added dropwise to the solution that step a is obtained under stirring, obtains mixed solution；
C. the obtained mixed solutions of step b are moved into the autoclave of 50mL, 140 DEG C of temperature, heating rate 1 DEG C/min, heat preservation for 24 hours, is naturally cooling to room temperature, then wash 3 times with absolute ethyl alcohol, and temperature 60 C is dried in vacuo to get to target The rodlike hybrid inorganic-organic bismuthino crystal (Fig. 2) of product.
Embodiment 3
A. by 0.103g Bi2S3It is dissolved in the hydroiodic acid that 2mL mass fractions are 57%, uses 0.45 μm of membrane filtration；
B. by 0.382g CH3NH3I is dissolved in 12mL absolute ethyl alcohols, adds 800 μ L pyridines, is added dropwise under at the uniform velocity stirring The solution that step a is obtained, obtains mixed solution；
C. the obtained mixed solutions of step b are moved into the autoclave of 50mL, 140 DEG C of temperature, heating rate 1 DEG C/min, heat preservation for 24 hours, is naturally cooling to room temperature, then wash 3 times with absolute ethyl alcohol, and temperature 60 C is dried in vacuo to get to target The hybrid inorganic-organic bismuthino crystal (Fig. 3) of product prismatic.

Claims (1)

1. a kind of synthetic method of morphology controllable hybrid inorganic-organic bismuthino crystal, it is characterised in that this method takes solvent heat Method prepares the hybrid inorganic-organic bismuthino crystal of different-shape by the way that different solvents are added, concrete operations follow these steps into Row：
Solvent is absolute ethyl alcohol：
A. by 0.103 g Bi2S3It is dissolved in the hydroiodic acid that 2 mL mass fractions are 57%, uses 0.45 μm of membrane filtration；
B. by 0.382 g CH3NH3I is dissolved in 12 mL absolute ethyl alcohols, is at the uniform velocity stirred the solution that lower a dropping step a is obtained, is obtained Mixed solution；
C. the obtained mixed solutions of step b are moved into the autoclave of 50 mL, 140 DEG C of temperature, 1 DEG C of heating rate/ Min keeps the temperature 24 h, is naturally cooling to room temperature, then washed 3 times with absolute ethyl alcohol, and temperature 60 C vacuum drying is produced to get to target The hybrid inorganic-organic bismuthino crystal of object hexagon；
Solvent is N,N-dimethylformamide：
A. by 0.103 g Bi2S3It is dissolved in the hydroiodic acid that 2 mL mass fractions are 57%, uses 0.45 μm of membrane filtration；
B. by 0.382 g CH3NH3I is dissolved in 12 mL absolute ethyl alcohols, adds 800 μ L n,N-Dimethylformamide, at the uniform velocity It is added dropwise to the solution that step a is obtained under stirring, obtains mixed solution；
C. the obtained mixed solutions of step b are moved into the autoclave of 50 mL, 140 DEG C of temperature, 1 DEG C of heating rate/ Min keeps the temperature 24 h, is naturally cooling to room temperature, then wash 3 times with absolute ethyl alcohol, and temperature 60 C is dried in vacuo to get to target The rodlike hybrid inorganic-organic bismuthino crystal of product；
Solvent is pyridine：
A. by 0.103 g Bi2S3It is dissolved in the hydroiodic acid that 2 mL mass fractions are 57%, uses 0.45 μm of membrane filtration；
B. by 0.382 g CH3NH3I is dissolved in 12 mL absolute ethyl alcohols, adds 800 μ L pyridines, and step is added dropwise under at the uniform velocity stirring The solution that rapid a is obtained, obtains mixed solution；
C. the obtained mixed solutions of step b are moved into the autoclave of 50 mL, 140 DEG C of temperature, 1 DEG C of heating rate/ Min keeps the temperature 24 h, is naturally cooling to room temperature, then wash 3 times with absolute ethyl alcohol, and temperature 60 C is dried in vacuo to get to target The hybrid inorganic-organic bismuthino crystal of product diamond shape.
CN201610397867.4A 2016-06-07 2016-06-07 A kind of synthetic method of morphology controllable hybrid inorganic-organic bismuthino crystal Expired - Fee Related CN106065494B (en)

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CN110144625B (en) * 2019-06-18 2021-01-05 山东科技大学 Growing method of red-light octagonal lead-free two-dimensional perovskite single crystal

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104372412A (en) * 2014-10-24 2015-02-25 山东大学 Methylamine halogenated plumbate compound large-size crystal growth method and device
CN104752065A (en) * 2015-04-13 2015-07-01 中国科学院新疆理化技术研究所 Preparing method of methyl amino bismuth iodide photovoltaic film
CN104911705A (en) * 2015-05-18 2015-09-16 陕西师范大学 Method for growing ABX3 perovskite single crystals in low-temperature solution

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104372412A (en) * 2014-10-24 2015-02-25 山东大学 Methylamine halogenated plumbate compound large-size crystal growth method and device
CN104752065A (en) * 2015-04-13 2015-07-01 中国科学院新疆理化技术研究所 Preparing method of methyl amino bismuth iodide photovoltaic film
CN104911705A (en) * 2015-05-18 2015-09-16 陕西师范大学 Method for growing ABX3 perovskite single crystals in low-temperature solution

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