CN109943329B - Two-dimensional mixed metal halide light-emitting semiconductor and preparation method and application thereof - Google Patents
Two-dimensional mixed metal halide light-emitting semiconductor and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of material preparation, and particularly relates to a two-dimensional mixed metal halide light-emitting semiconductor with a molecular formula of [ (Me)2‑DABCO]Ag2PbBr6Belonging to the monoclinic system, P21Space group, cell parameters
β＝91.6700(10)°，
And the mixed metal halide emits red light with the wavelength of 711nm under the excitation of ultraviolet light with the wavelength of 316nm, the Stock shift is 395nm, the half-peak width is 239nm, the luminous intensity is in a linear relation with the temperature within 80-200K, and the mixed metal halide can be used as a fluorescent temperature sensing material in a low-temperature region.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a two-dimensional mixed metal halide light-emitting semiconductor and a preparation method and application thereof.
Background
Two-dimensional materials are valued by scientists and have a wide application prospect due to their unique layered structure, physical and chemical properties. Although two-dimensional graphene layered materials have been widely used in the fields of electronics and new energy, their zero band gap has seriously hindered the application of graphene in the field of semiconductor photovoltaics. In order to develop a graphene material with semiconductor characteristics, scientists modify and improve the crystal structure and the energy band structure of graphene by means of doping, compounding and the like, and adjust the semiconductor characteristics of graphene. In addition, a large number of scientific research teams start with the graphene laminated structure to develop novel two-dimensional materials with similar graphene structures. The lead halide has a two-dimensional layered structure, and the structural unit of the lead halide is PbX6(X ═ Cl, Br, I) octahedral units, which form two-dimensional layers by sharing halogen atoms between them, and are stacked by van der waals forces between the layers. However, the traditional lead halide material has simple structure and PbX6The octahedral connection mode is single, and the modification is difficult from the structural chemistry perspective.
In recent years, organic-inorganic hybrid lead halide materials have attracted extensive research interest to scientists due to their abundant structural types and adjustable physicochemical properties. In particular having CH3NH3PbX3Preparation process of organic-inorganic hybrid halide with perovskite structureThe structure is simple, the structure is various, the photoelectric property is excellent, and the method has very important research significance and application value in the fields of luminescent semiconductors, solar cells and the like. However, the metal Pb can seriously pollute the environment, and the halide of the Pb is not stable, so the application prospect of the perovskite-structured Pb halide is seriously influenced. In order to solve this problem, the development of non-Pb halides or the reduction of Pb content has very important research significance for the application of organic-inorganic hybrid metal halides.
Disclosure of Invention
Aiming at the scientific difficult problems of environmental pollution and poor stability of the traditional organic-inorganic hybrid Pb halide, the invention introduces the transition metal Ag and provides a two-dimensional mixed metal halide light-emitting semiconductor and a preparation method and application thereof.
The molecular formula of the two-dimensional mixed metal halide light-emitting semiconductor is [ (Me)2-DABCO]Ag2PbBr6((Me)2-DABCO ═ N, N-dimethyl-triethylenediamine), the compound belonging to the monoclinic system, P21Space group, cell parameters
β＝91.6700(10)°,
Z＝4。
The two-dimensional mixed metal halide light-emitting semiconductor has the following structural characteristics: the compound is [ AgBr ]4]Tetrahedron and [ PbBr6]Two-dimensional [ Ag ] with octahedra connected by shared Br atoms2PbBr6]2Layer, [ (Me)2-DABCO]The + organic cations are filled between the two-dimensional layers and are connected through hydrogen bonds to form a three-dimensional supramolecular structure.
The preparation method of the two-dimensional mixed metal halide light-emitting semiconductor comprises the following steps:
i) weighing DA according to the molar ratio of 1-1.3: 2-2.4: 1-1.2: 3-5BCO、AgBr、PbBr2Adding KBr serving as a reaction raw material into a mixed solvent of 4-5 mL of acetonitrile, 0.5-1 mL of hydrobromic acid and 1-2 mL of methanol, filling the mixed solution into a polytetrafluoroethylene inner container, and sealing in a reaction kettle;
ii) placing the sealed stainless steel reaction kettle into a drying box for reaction at 180 ℃ for 4-6 days, and naturally cooling to room temperature;
iii) opening the reaction kettle, filtering the mixed solution, washing the yellow block obtained by filtering with distilled water for 2-3 times, and drying in a vacuum oven at 60 ℃ for 3-4 hours to obtain a finished product [ (Me)2-DABCO]Ag2PbBr6Yellow crystals of (2), yield 21%.
The two-dimensional mixed metal halide provided by the invention can absorb all ultraviolet rays and a part of visible light, has stronger optical absorption between 200-400nm, has a band gap of 2.5eV, belongs to a semiconductor material, and can be excited by ultraviolet rays or purple light to emit fluorescence.
The two-dimensional mixed metal halide provided by the invention can emit red light with the wavelength of 711nm at room temperature under the excitation of 316nm ultraviolet rays, the Stock displacement is 395nm, the half-peak width is 239nm, and the two-dimensional mixed metal halide can be used as a red light semiconductor.
The luminous intensity of the two-dimensional mixed metal halide luminescent material provided by the invention can be obviously changed along with the change of the external temperature. The intensity of the emission peak is continuously reduced in the temperature range from 300K to 80K, the luminous intensity is linearly changed with the temperature in the range from 80K to 200K, and the change relation is that the relation is-0.00754T + 1.5987. The fluorescence intensity is sensitive to the temperature change, the change value can reach about 90 percent, the sensitivity is 8.9 at 200K, and the fluorescence intensity is far greater than that of all the rare earth complexes discovered at present. Therefore, the mixed metal halide semiconductor provided by the invention can be used as a red light temperature sensing material and applied to temperature detection in non-contact working environments of organisms, medical diagnosis and the like.
Compared with the prior art, the invention has the following beneficial effects.
The organic-inorganic hybrid two-dimensional mixed metal halide semiconductor material provided by the invention has the advantages of simple preparation process, low price, linear relation between fluorescence intensity and temperature at low temperature, high sensitivity and fluorescence temperature sensing effect, and can be used as a red light temperature sensing material for in vivo and medical diagnosis.
Drawings
FIG. 1 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6The crystal structure of (1);
FIG. 2 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6Powder diffraction pattern of (a);
FIG. 3 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6Ultraviolet-visible absorption spectrum of (1);
FIG. 4 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6Thermogravimetric analysis of (a);
FIG. 5 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6Excitation and emission spectra of (a);
FIG. 6 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6Emission spectra at different temperatures;
FIG. 7 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6The curve of the fluorescence intensity with temperature;
FIG. 8 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6Sensitivity of fluorescence intensity with temperature.
Mixed metal halides [ (Me) in FIGS. 1-82-DABCO]Ag2PbBr6Prepared as in example 1.
Example 1
DABCO (0.5mmol), AgBr (1.2mmol) and PbBr were weighed in a molar ratio of 1:2:1:32(0.5mmol) and KBr (2.0mmol) as reaction raw materials are added into a mixed solvent of 4mL acetonitrile, 1mL hydrobromic acid and 1mL methanol, the mixed solution is filled into a polytetrafluoroethylene inner container and sealed in a reaction kettle, the mixture reacts in a drying oven at 160 ℃ for 6 days, the mixture is naturally cooled to room temperature, the mixed solution is filtered, the light yellow color block obtained by filtering is washed by distilled water for 2 to 3 times, and the mixture is dried in a vacuum oven at 60 ℃ for 3 hours, so that the light yellow color block can be obtainedTo obtain [ (Me)2-DABCO]Ag2PbBr6Yellow crystals of (4).
Example 2
DABCO (0.5mmol), AgBr (0.9mmol) and PbBr were weighed in a molar ratio of 1:2.4:1:42(0.4mmol) and KBr (1.9mmol) as reaction raw materials are added into a mixed solvent of 4mL acetonitrile, 1mL hydrobromic acid and 1mL methanol, the mixed solution is filled into a polytetrafluoroethylene inner container and sealed in a reaction kettle, the mixture reacts in a drying oven at 180 ℃ for 4 days, the mixture is naturally cooled to room temperature, the mixed solution is filtered, the light yellow color block obtained by filtering is washed by distilled water for 2 to 3 times and dried in a vacuum oven at 60 ℃ for 4 hours, and then [ (Me) can be obtained2-DABCO]Ag2PbBr6Yellow crystals of (4).
In FIG. 2, the yellow bulk crystals after the reaction in example 1 were collected, washed, dried, and then ground, and the diffraction data collected by X-ray powder diffraction was consistent with the diffraction data obtained by fitting the single crystal structure, indicating that all the yellow crystals were [ (Me)2-DABCO]Ag2PbBr6The purity can reach 100%;
the yellow bulk crystals after the reaction in example 1 were collected, washed, dried and ground, and as shown in FIG. 2, the diffraction data collected by X-ray powder diffraction was consistent with the diffraction data obtained by fitting the single crystal structure, indicating that all the yellow crystals were [ (Me)2-DABCO]Ag2PbBr6The purity can reach 100%;
the sensitivity of fluorescence temperature detection is calculated by the following formula:
sr represents the sensitivity of the compound to be detected,
represents the range of the luminous intensity of the emitted light,
represents the temperature range and I represents the luminescence intensity.
FIG. 1 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6Crystal structure diagram of (1): all Ag atoms are in four coordination, the Pb atom is in six coordination, [ AgBr ]4]The tetrahedra being joined by sharing Br atoms to form Ag4Br12One-dimensional chain, then passing PbBr in between6Octahedral linkage to form two dimensions [ AgPb ]2Br6]2-a layer;
FIG. 2 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6The diffraction pattern of the polycrystalline powder of (1) is the same as the data of the single crystal structure simulation, indicating that the polycrystalline powder is a pure complex mixed metal halide [ (Me)2-DABCO]Ag2PbBr6The purity is close to 100%;
FIG. 3 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6The halide has stronger optical absorption between 200 and 400nm, the band gap is 2.77eV, and the halide belongs to a semiconductor material;
FIG. 4 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6In N2The microporous material is heated to a thermogravimetric curve of 800 ℃ from room temperature in the atmosphere, and loses weight from 300 ℃, which shows that the microporous material can be heated to 300 ℃, has better thermal stability, and can meet the use requirement as a semiconductor luminescent material;
FIG. 5 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6The Stock shift is 395nm and the half-peak width is 239nm in the excitation spectrum and the emission spectrum at room temperature.
FIG. 6 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6The fluorescence emission spectra at different temperatures have the strongest emission intensity at 80K and the weakest emission intensity at 300K, and the luminous intensity is increased along with the reduction of the temperature;
FIG. 7 shows mixed metal halides [ (Me)2-DABCO]Ag2PbBr6The conversion relation between the emission peak intensity and the temperature is that the fluorescence intensity and the temperature are in a linear relation within the range of 80-200K, and the calculation formula is Imax-0.00754 × T +1.5987, wherein ImaxRepresents the luminous intensity and T represents the temperature.
FIG. 8 shows the sensitivity of the change in fluorescence intensity with temperature, which was 8.9 at 200K.
Claims (9)
1. A two-dimensional mixed metal halide light-emitting semiconductor is characterized in that: the molecular formula is [ (Me) 2-DABCO]Ag 2 PbBr 6, (Me) 2-DABCO ═ N, N-dimethyl-trivinyldiamine, the compound belonging to the monoclinic system, P21Space group, unit cell parameters a =8.9174 (9), b =14.4304 (15), c =15.2565 (16), β ═ 91.6700(10) ° a, V =1962.4 (4) a3，Z＝4。
2. A two-dimensional mixed metal halide light emitting semiconductor as claimed in claim 1, wherein: the compound is [ AgBr ]4 ]Tetrahedron and [ PbBr6]Two-dimensional [ Ag ] with octahedra connected by shared Br atoms2PbBr6]2-Layer, [ (Me)2 -DABCO]+The organic cations are filled between the two-dimensional layers and are connected through hydrogen bonds to form a three-dimensional supramolecular structure.
3. The method of preparing a two-dimensional mixed metal halide light-emitting semiconductor as claimed in claim 1, wherein: the solvent thermal reaction synthesis method comprises the following steps: with DABCO, AgBr, PbBr2And KBr is used as a reaction raw material, the obtained mixture is added into a mixed solution of acetonitrile, hydrobromic acid and methanol, the mixed solution is filled into a polytetrafluoroethylene inner container, the polytetrafluoroethylene inner container is sealed in a reaction kettle and placed in a drying box for heating reaction, the reaction is naturally cooled to room temperature after the reaction, the mixed solution is filtered, the light yellow color block obtained by filtering is washed by distilled water, and then the mixture is placed in a vacuum oven for drying, so that a finished product is obtained.
4. The method according to claim 3, wherein: DABCO, AgBr, PbBr2And the molar ratio of the used amount of KBr is as follows: 1-1.3: 2-2.4: 1-1.2: 3-5.
5. The method according to claim 3, wherein: the dosage of the acetonitrile, the hydrobromic acid and the methanol is respectively 4-5 mL, 0.5-1 mL and 1-2 mL.
6. The method according to claim 3, wherein: the reaction kettle is arranged in a drying box at the temperature of 160 ℃ and 180 ℃ for 4-6 days.
7. The method according to claim 3, wherein: the drying temperature in the vacuum oven is 60 ℃, and the drying time is 3-4 hours.
8. Use of the two-dimensional mixed metal halide light-emitting semiconductor prepared by the preparation method according to any one of claims 3 to 7, wherein: when the compound is used as a temperature sensing material for temperature detection in a non-contact working environment, the luminous intensity of the compound is in a linear relation with the temperature within the range of 80-200K, and the relation is represented by the formula I-0.00754T + 1.5987.
9. Use of a two-dimensional mixed metal halide light emitting semiconductor as claimed in claim 8, wherein: under the excitation of ultraviolet rays with the wavelength of 316nm, red light with the wavelength of 711nm is emitted, the Stock shift is 395nm, and the half-peak width is 239.
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| CN105562094A (en) * | 2015-12-29 | 2016-05-11 | 济宁学院 | Micro-porous transition metal halide visible photocatalysis material, and preparation method and application thereof |
| CN107418570A (en) * | 2017-07-03 | 2017-12-01 | 苏州虹霞晶体科技有限公司 | A kind of zero dimension perovskite structure high efficient luminous material and reversal temperature production method |
| CN109546007A (en) * | 2018-11-02 | 2019-03-29 | 南京邮电大学 | A kind of light emitting diode and preparation method thereof based on two-dimentional lead halide perovskite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105562094A (en) * | 2015-12-29 | 2016-05-11 | 济宁学院 | Micro-porous transition metal halide visible photocatalysis material, and preparation method and application thereof |
| CN107418570A (en) * | 2017-07-03 | 2017-12-01 | 苏州虹霞晶体科技有限公司 | A kind of zero dimension perovskite structure high efficient luminous material and reversal temperature production method |
| CN109546007A (en) * | 2018-11-02 | 2019-03-29 | 南京邮电大学 | A kind of light emitting diode and preparation method thereof based on two-dimentional lead halide perovskite material |
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