CN112251815B - One-dimensional DMAPbI3Method for growing large single crystal - Google Patents

One-dimensional DMAPbI3Method for growing large single crystal Download PDF

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CN112251815B
CN112251815B CN202010953206.1A CN202010953206A CN112251815B CN 112251815 B CN112251815 B CN 112251815B CN 202010953206 A CN202010953206 A CN 202010953206A CN 112251815 B CN112251815 B CN 112251815B
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dmapbi
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高凯歌
王一鸣
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Yangzhou University
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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
    • C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
    • 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
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Abstract

The invention relates to a one-dimensional DMAPbI in the field of organic-inorganic hybrid perovskite crystal materials3A method of growing a large single crystal, the method comprising the steps of: 1) benzylamine and PbI2Stirring and dissolving in DMF to form clear yellow solution; 2) dripping the hydriodic acid solution into the solution, and then dripping the phosphorous acid aqueous solution to stabilize the hydriodic acid, wherein the finally formed solution is a clear yellow solution; 3) heating the obtained yellow solution at 55-65 deg.C to volatilize liquid, and decomposing DMF to obtain dimethylamine, to obtain DMAPbI3A saturated solution; 4) volatilizing the solvent from the obtained solution at room temperature, and growing large yellow single crystals after 10-30 days. The invention grows the one-dimensional DMAPbI with the size of 2 mm multiplied by 4 mm multiplied by 8 mm by an improved solution method3The large single crystal can be used as a photoelectric material and can be well applied to the field of photoelectric conversion.

Description

One-dimensional DMAPbI3Method for growing large single crystal
Technical Field
The invention relates to a perovskite crystal, in particular to the technical field of preparation of organic and inorganic hybrid perovskite crystal materials.
Background
In the prior art, organic and inorganic hybrid perovskites are receiving much attention because of their excellent photoelectric effects. Wherein methylamine lead iodide (MAPbI) is used3) The photoelectric efficiency of the representative three-dimensional organic-inorganic hybrid perovskite solar cell reaches 22 percent, and the solar cell can be comparable to a silicon solar cell. One-dimensional organic-inorganic hybrid perovskites have received much attention because of their good moisture tolerance and excellent optoelectronic properties. In the one-dimensional chain compound, the one-dimensional inorganic chains are separated by organic ions to form a quantum line structure. In such a quantum wire, carriers are confined in a one-dimensional inorganic framework. Therefore, the research on the one-dimensional organic-inorganic hybrid perovskite has considerable application prospect.
DMAPbI3 ((CH3)2NH2PbI3) Is a one-dimensional organic-inorganic hybrid perovskite comprising [ PbI6]The octahedron is coplanar to form infinite long one-dimensional chains, and dimethylamine ions ((CH) are arranged between the one-dimensional chains3)2NH2 +) And (4) isolating. Due to the defect formed by one-dimensional chain fracture, the one-dimensional organolead-iodine perovskite can be in the direction along the chainLong, but hardly thick in the direction perpendicular to the chain. Literature reported DMAPbI3The shortest side of the single crystal is only less than 0.2 mm in size. The application of the material in photoelectric conversion is limited.
Disclosure of Invention
The invention aims to provide a one-dimensional DMAPbI3The method for growing the large single crystal can prepare the one-dimensional lead-iodine-calcium-titanium ore large single crystal.
Therefore, the technical scheme provided by the invention is as follows: a method for growing a one-dimensional DMAPbI3 large single crystal comprises the following steps:
1) benzylamine and PbI2Dissolving in DMF (N, N-dimethylformamide) with stirring to form a clear yellow solution;
2) dripping the hydriodic acid solution into the solution, and then dripping the phosphorous acid aqueous solution to stabilize the hydriodic acid, wherein the finally formed solution is a clear yellow solution;
3) heating the obtained yellow solution at 55-65 deg.C to volatilize liquid, and decomposing DMF to obtain dimethylamine, to obtain DMAPbI3A saturated solution;
4) volatilizing the solvent from the obtained solution at room temperature, and growing large yellow single crystals after 10-30 days.
Further, the benzylamine and PbI2The net mass ratio of DMF, hydroiodic acid and phosphorous acid is as follows: (21-107): 426: (4700-9440): (4200-8500):(2000-4000).
The mass concentration of HI in the hydroiodic acid was 57%. The phosphorous acid mass concentration in the phosphorous acid aqueous solution is 50%. The hydriodic acid and the phosphorous acid with the concentrations are easy to obtain and convenient to manufacture.
In the present invention, DMF + HI + H2O → DMAI + HCOOH, dynamic reaction to dimethylamine ion, followed by DMAI + PbI2Reaction to obtain DMAPbI3And (3) single crystal. The solvent adopted by the invention is not a single solvent, but a dynamic solvent formed by DMF and hydriodic acid, and the solvent comprises DMF, hydriodic acid solution, formic acid and water. Benzylamine is also added into the solution to assist the one-dimensional DMAPbI3And (4) growing a large single crystal. Benzylamine will react with excess hydriodic acid in the solutionIn addition, a benzylamine hydrochloride solution is formed, which can be mixed with PbI2Clusters are formed. Benzylamine assisted DMAPbI3The mechanism for growing large single crystals may be: benzylamine hydrochloride with PbI2Reacted to form (benzylammonium)2PbI4(BA2PbI4) However, in the dynamic solution system of the present invention, BA2PbI4Has a much higher saturation solubility than DMAPbI3So that only DMAPbI is present in the initial stage of crystal growth in solution3Can grow and grow. Because the crystals are imperfect, DMAPbI grows out of solution3There are a large number of one-dimensional chain-breaking defects, which make it difficult to grow a single crystal larger. And benzylamine can be present by forming BA2PbI4And redissolved DMAPbI in solution3The more defective part of the crystal, thus promoting DMAPbI3Growing the single crystal to obtain the unprecedented one-dimensional organic lead iodine large single crystal. Compared with the prior art, the invention has the beneficial effects that: the invention grows the one-dimensional DMAPbI with the size of 2 mm multiplied by 4 mm multiplied by 8 mm by an improved solution method3Large single crystals, which are the largest size one-dimensional lead-iodine perovskite single crystals known to date. The obtained large-size one-dimensional lead-iodine perovskite single crystal can be used as a photoelectric material and can be well applied to the field of photoelectric conversion. The one-dimensional perovskite has a unique electro-optical effect due to the quantum confinement effect. Unlike perovskites, which require extremely small dimensions to achieve high efficiency light emission, one-dimensional perovskites can achieve high efficiency light emission even if they are large in size. Compared with the three-dimensional lead-iodine perovskite, the one-dimensional lead-iodine perovskite has higher stability, so that the one-dimensional lead-iodine perovskite has higher application potential in the field of luminescence.
Drawings
FIG. 1 is a photograph of a large single crystal of 1-dimensional DMAPbI3 grown by the present invention.
FIG. 2 shows a hysteresis loop of a grown large single crystal at a temperature of 231K.
FIG. 3 is a schematic diagram showing the temperature-varying pyroelectric current of a large single crystal grown and the polarization value obtained by integrating the pyroelectric current with temperature.
Detailed Description
Example 1
21 mg of chemically pure benzylamine and 461 mg of chemically pure PbI2Dissolved in 9.44g of chemically pure DMF with stirring to form a clear yellow solution, and then 14.91g of hydriodic acid solution (HI concentration 57% by mass) was added dropwise to the solution, and 8g of an aqueous phosphorous acid solution (phosphorous acid concentration 50% by mass) was added dropwise to the solution to stabilize the hydriodic acid. The resulting solution was a clear yellow solution. Heating the solution at 60 deg.C for 5-24 hr to volatilize the liquid and decompose dimethylamine to obtain DMAPbI3The solution is saturated, then the solvent is volatilized from the obtained solution at room temperature, and large yellow single crystals grow after 10 to 30 days.
The following Table is DMAPbI in this example3The saturated solution grows yellow single crystal size through different times:
Figure DEST_PATH_IMAGE002
as shown in the above table, DMAPbI is present between 5 and 10 days3The single crystal has smaller size, larger size after 10 days, and then gradually grows and grows, but the change is not large after 20 days, and the value is more reasonable within 10-30 days.
Example 2
107 mg of chemically pure benzylamine and 461 mg of chemically pure PbI2Dissolved in 4.7g of chemically pure DMF with stirring to form a clear yellow solution, 7.38g of hydroiodic acid solution (HI concentration 57% by mass) were added dropwise to the solution, and 4g of an aqueous phosphorous acid solution (phosphorous acid concentration 50% by mass) were added dropwise to the solution to stabilize the hydroiodic acid. The resulting solution was a clear yellow solution. Heating the solution on a 65 ℃ heating table to volatilize the liquid, and decomposing dimethylamine to obtain DMAPbI3The solution is saturated, then the solvent is volatilized from the obtained solution at room temperature, and large yellow single crystals grow after 10 to 30 days.
Example 3
60 mg of chemically pure benzylamine and 461 mg of chemically pure PbI2Dissolved in 7.07g of chemically pure DMF with stirring,a clear yellow solution was formed, and then 11.14g of hydriodic acid solution (HI concentration 57% by mass) was dropped into the solution, and 6g of phosphorous acid aqueous solution (phosphorous acid concentration 50% by mass) was dropped into the solution to stabilize the hydriodic acid. The resulting solution was a clear yellow solution. Heating the solution on a heating table at 55 ℃ to volatilize the liquid, and decomposing dimethylamine to obtain DMAPbI3The solution is saturated, then the solvent is volatilized from the obtained solution at room temperature, and large yellow single crystals grow after 10 to 30 days.
Example 4
87 mg of chemically pure benzylamine and 461 mg of chemically pure PbI2Dissolved in 9.44g of chemically pure DMF with stirring to form a clear yellow solution, 7.38g of hydriodic acid solution (HI concentration 57% by mass) were added dropwise to the solution, and 6g of an aqueous phosphorous acid solution (phosphorous acid concentration 50% by mass) were added dropwise to the solution to stabilize the hydriodic acid. The resulting solution was a clear yellow solution. Heating the solution on a heating table at 55 deg.C for about 8-15 hr to volatilize the liquid and decompose dimethylamine to obtain DMAPbI3The solution is saturated, then the solvent is volatilized from the obtained solution at room temperature, and large yellow single crystals grow after 10 to 30 days.
Comparative example
With dimethylamine iodine (CH)3NH2CH3I) As a raw material, with PbI2Reacting according to a molar ratio of 1:1, dissolving in DMF, and obtaining the following reaction formula: CH (CH)3NHCH3+HI+PbI2→DMAPbI3Volatilizing the solvent from the solution obtained by the reaction at room temperature, and growing a yellow single crystal after 30 days, namely DMAPbI3。
DMAPbI obtained in the above examples and comparative examples3The dimensions after 30 days of growth are shown in the table below:
Figure DEST_PATH_IMAGE004
the above table shows that one-dimensional DMAPbI can be obtained by the process of the invention3Large single crystals, which cannot be achieved by the comparative example.
FIG. 1 is a photograph of a large single crystal of 1-dimensional DMAPbI3 grown by the present invention.
The large single crystal grown in FIG. 2 was measured for a measured hysteresis loop at a temperature of 231K. Surface of hysteresis loop DMAPbI3Is ferroelectric at low temperature and has a spontaneous polarization value of about 0.2 μ C/cm2.
FIG. 3 is a schematic diagram showing the temperature variation of a large crystal grown by measuring a temperature-variable pyroelectric current and the polarization value obtained by integrating the pyroelectric current with the temperature. The pyroelectric current test shows that the temperature is below 263K, and DMAPbI3Is ferroelectric.
The present invention is not limited to the above-mentioned embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts according to the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.

Claims (3)

1. One-dimensional DMAPbI3A method for growing a large single crystal, characterized by comprising the steps of:
1) benzylamine and PbI2Stirring and dissolving in DMF to form clear yellow solution;
2) dripping the hydriodic acid solution into the solution, and then dripping the phosphorous acid aqueous solution to stabilize the hydriodic acid, wherein the finally formed solution is a clear yellow solution;
the benzylamine and PbI2The net mass ratio of DMF, hydroiodic acid and phosphorous acid is as follows: (21-107): 461: (4700-9440): (4200-8500): (2000-4000);
3) heating the obtained yellow solution at 55-65 deg.C to volatilize liquid, and decomposing DMF to obtain dimethylamine, to obtain DMAPbI3A saturated solution;
4) volatilizing the solvent from the obtained solution at room temperature, and growing large yellow single crystals after 10-30 days.
2. The one-dimensional DMAPbI of claim 13A method for growing a large single crystal, comprising: the hydriodic acidThe HI mass concentration in (b) was 57%.
3. The one-dimensional DMAPbI of claim 13A method for growing a large single crystal, comprising: the phosphorous acid mass concentration in the phosphorous acid aqueous solution is 50%.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104131352A (en) * 2014-07-17 2014-11-05 南京信息工程大学 Preparation method of large-sized perovskite structure CH3NH3PbI3 crystal
CN107833972A (en) * 2017-10-31 2018-03-23 武汉工程大学 A kind of preparation method of organic inorganic hybridization perovskite
CN110318093A (en) * 2019-04-30 2019-10-11 吕梁学院 A method of efficiently preparing hybrid inorganic-organic perovskite seed crystal

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104131352A (en) * 2014-07-17 2014-11-05 南京信息工程大学 Preparation method of large-sized perovskite structure CH3NH3PbI3 crystal
CN107833972A (en) * 2017-10-31 2018-03-23 武汉工程大学 A kind of preparation method of organic inorganic hybridization perovskite
CN110318093A (en) * 2019-04-30 2019-10-11 吕梁学院 A method of efficiently preparing hybrid inorganic-organic perovskite seed crystal

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
On the Demystification of "HPbI3" and the Peculiarities of the Non-innocent Solvents H2O and DMF;Michael Daub等;《Journal of Inorganic and General Chemistry》;20180824;第644卷;第1393-1400页 *
Single Crystal Formamidinium Lead Iodide (FAPbI 3 ): Insight into the Structural, Optical, and Electrical Properties;Qifeng Han 等;《Advanced Materials》;20160120;第28卷;第2253-2258页 *

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