CN115710495A - Two-dimensional non-lead perovskite material and preparation method and application thereof - Google Patents
Two-dimensional non-lead perovskite material and preparation method and application thereof Download PDFInfo
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- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 33
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- 238000001816 cooling Methods 0.000 claims description 21
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- 238000006243 chemical reaction Methods 0.000 claims description 18
- 230000005284 excitation Effects 0.000 claims description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
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- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 9
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- 150000007524 organic acids Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- 238000002441 X-ray diffraction Methods 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 238000006862 quantum yield reaction Methods 0.000 claims description 2
- 238000012876 topography Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- -1 tin halide Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 150000002892 organic cations Chemical class 0.000 abstract description 2
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 8
- 239000005642 Oleic acid Substances 0.000 description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 8
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
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- 238000000295 emission spectrum Methods 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
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- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
The invention belongs to the technical field of luminescent materials, and particularly relates to a two-dimensional non-lead perovskite material, and a preparation method and application thereof, wherein the molecular formula of the two-dimensional non-lead perovskite material is (C) 18 H 35 NH 3 ) 2 SnX 4 Wherein, X is a halogen element and is selected from one, two or three of Cl, br and I. The two-dimensional non-lead perovskite material has good luminescence performance, and the organic cations have better protection effect on photoactive tin halide structural units, so that the two-dimensional tin halide perovskite has higher stability than the three-dimensional tin halide perovskite.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a two-dimensional non-lead perovskite material (C) 18 H 35 NH 3 ) 2 SnX 4 And a preparation method and application thereof.
Background
In recent years, lead-based perovskite materials are widely concerned by researchers at home and abroad, and the materials show good application prospects in the fields of optoelectronic devices such as solar cells, photodetectors, light emitting diodes and the like due to excellent performances such as high light absorption coefficient, long carrier service life, simple preparation process and the like. However, the commercial use of lead has been limited due to its toxicity.
In order to solve the toxicity problem of lead, currently, considering that the tin-based system of the same main group has the characteristics of no toxicity, electronic structure similar to lead, adjustable band gap, low exciton binding energy and the like, the non-toxic perovskite material based on the tin-based system is developed and is based on ASnI 3 [A＝CH 3 NH 3 、CH(NH 2 ) 2 Or Cs]Has proven to be useful in high efficiency solar cells; however, sn (II) is easily oxidized and has poor stability, which hinders the development and application of Sn (II).
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a two-dimensional non-lead perovskite material with the molecular formula of (C) 18 H 35 NH 3 ) 2 SnX 4 Wherein, X is a halogen element and is selected from one, two or three of Cl, br and I.
Preferably, said (C) 18 H 35 NH 3 ) 2 SnX 4 Is (C) 18 H 35 NH 3 ) 2 SnCl 4 、(C 18 H 35 NH 3 ) 2 SnBr 4 、(C 18 H 35 NH 3 ) 2 SnI 4 、(C 18 H 35 NH 3 ) 2 Sn(Cl x1 Br 1-x1 ) 4 、(C 18 H 35 NH 3 ) 2 Sn(Cl x2 I 1-x2 ) 4 Or (C) 18 H 35 NH 3 ) 2 Sn(Br x3 I 1-x3 ) 4 And x1, x2 and x3 are independently selected from 1, 2 or 3.
Preferably, the two-dimensional non-lead perovskite material is a sheet structure.
Preferably, the two-dimensional non-lead perovskite material is a micro-sheet structure stacked vertically together.
Preferably, the two-dimensional non-lead perovskite material has a size of no more than 50 microns, preferably from 0.1 to 20 microns, more preferably from 0.1 to 10 microns, for example 0.1 microns, 0.5 microns, 1 micron, 2 microns.
According to an embodiment of the present invention, the two-dimensional non-lead perovskite material has an electron-microscopic topography substantially as shown in fig. 1.
According to an embodiment of the invention, the two-dimensional non-lead perovskite material has an XRD pattern substantially as shown in fig. 2.
According to an embodiment of the present invention, the two-dimensional non-lead perovskite material has orange or red light emission substantially as shown in fig. 3 under irradiation of excitation light having a wavelength of 300-365 nm.
Preferably, said (C) 18 H 35 NH 3 ) 2 SnCl 4 Under ultraviolet light excitation (e.g. 300 nm), there is orange light emission, for example having a wavelength of 616 nm.
Preferably, said (C) 18 H 35 NH 3 ) 2 SnBr 4 Under ultraviolet light excitation (e.g. 346 nm), there is orange light emission, for example having a wavelength of 619 nm.
Preferably, said (C) 18 H 35 NH 3 ) 2 SnI 4 Under ultraviolet light excitation (e.g. 365 nm), there is red emission, for example red emission with a wavelength of 666 nm.
Preferably, theC 18 H 35 NH 3 ) 2 Sn(Cl x1 Br 1-x1 ) 4 Under ultraviolet light excitation (e.g. 341 nm), there is orange light emission, for example having a wavelength of 624 nm.
Preferably, said (C) 18 H 35 NH 3 ) 2 Sn(Cl x2 I 1-x2 ) 4 Under ultraviolet light excitation (e.g. 365 nm), there is red emission, for example red emission with a wavelength of 666 nm.
Preferably, said (C) 18 H 35 NH 3 ) 2 Sn(Br x3 I 1-x3 ) 4 Under ultraviolet light excitation (317 nm for example), the material has orange light emission and orange light emission with the wavelength of 642 nm.
According to an embodiment of the invention, the two-dimensional non-lead perovskite material has a single exponential fluorescence decay lifetime substantially as shown in fig. 4.
According to an embodiment of the invention, the two-dimensional non-lead perovskite material has a fluorescence quantum yield of 1-90%, preferably 60-90%, for example 85%.
The invention also provides a preparation method of the two-dimensional non-lead perovskite material, which comprises the following steps:
1) Mixing a tin source, organic amine, organic acid and octadecene to obtain a mixed solution 1;
2) And adding a halogen source into the mixed solution 1 for reaction to obtain the two-dimensional non-lead perovskite material.
According to an embodiment of the invention, the molar volume ratio of the tin source to the organic amine in step 1) is (0.02-0.5) mmol, (0.5-1.5) ml, preferably (0.1-0.4) mmol, (0.8-1.2) ml, e.g. 1ml, which is 0.3 mmol.
According to an embodiment of the present invention, in the step 1), the volume ratio of the organic amine, the organic acid and the octadecene is (0.5-1.5): (5-15), preferably (0.8-1.2): (8-12), for example, 1.
According to an embodiment of the invention, the molar ratio of tin source to halogen source is (0-2): 0-20) and does not comprise a value of 0, preferably (0.9-1): 2-15, such as 0.9.
According to an embodiment of the present invention, the common concentration of the tin source, the halogen source, and the organic amine in the mixed solution 1 is not more than 25mol%, preferably 5 to 20mol%, and more preferably 10 to 18mol%, for example, the synthesis concentration is 13mol%, 14mol%, 17mol%.
According to an embodiment of the invention, the tin source is selected from one, a mixture of two or more of stannous oxalate, stannous octoate, stannous oxide, tin acetate and dibutyltin, for example stannous octoate.
According to an embodiment of the invention, the organic amine is R 1 NH 2 Wherein, said R 1 Is selected from C 4-22 Is selected from the group consisting of 4-20 More preferably, selected from C 4-18 For example, one or a mixture of two or more of butylamine, n-octylamine, dodecylamine, octadecylamine and oleylamine, for example, oleylamine.
According to an embodiment of the invention, the organic acid is R 2 COOH, wherein, the R 2 Is selected from C 6-20 Is selected from the group consisting of 7-17 The straight-chain or branched alkyl group of the alkyl group is, for example, one of octanoic acid, dodecanoic acid, oleic acid, or a mixture of two or more thereof, such as oleic acid.
According to an embodiment of the invention, the halogen source is selected from one, two or a mixture of three of hydrochloric acid, hydrobromic acid and hydroiodic acid, preferably hydroiodic acid, hydrochloric acid or hydrobromic acid.
According to an embodiment of the invention, the mixing in step 1) is carried out under an inert atmosphere and heating, preferably by passing nitrogen and/or argon, for example nitrogen.
According to an embodiment of the invention, the temperature of the mixing in step 1) is 80-200 ℃, preferably the temperature of the mixing is 100-150 ℃, exemplary 110 ℃, 120 ℃, 130 ℃, 140 ℃.
Preferably, the mixing in step 1) is performed under stirring.
According to the embodiment of the invention, before heating to 80-200 ℃ in the step 1), the method further comprises the steps of introducing nitrogen into the reaction raw materials and stirring for 10-30 minutes.
Preferably, the mixing time after heating is from 0.5 to 1.5 hours, preferably from 1 to 1.2 hours, for example 1 hour.
According to the embodiment of the invention, after the halogen source and the mixed solution 1 react in the step 2), the method further comprises a step of quick cooling.
According to an embodiment of the present invention, the step 2) comprises the steps of: and adding a halogen source into the mixed solution 1, reacting completely, and then quickly cooling to obtain the two-dimensional non-lead perovskite material.
Preferably, hydrochloric acid is added into the mixed solution 1 for reaction, and the two-dimensional non-lead perovskite material (C) is obtained by rapid cooling after the reaction is finished 18 H 35 NH 3 ) 2 SnCl 4 。
Preferably, hydrobromic acid is added into the mixed solution 1 for reaction, and the two-dimensional non-lead perovskite material (C) is obtained by rapid cooling after the reaction is finished 18 H 35 NH 3 ) 2 SnBr 4 。
Preferably, hydroiodic acid is added into the mixed solution 1 for reaction, and the mixture is quickly cooled after the reaction is finished to obtain the two-dimensional non-lead perovskite material (C) 18 H 35 NH 3 ) 2 SnI 4 。
Preferably, the mixed solution of hydrochloric acid and hydrobromic acid is added into the mixed solution 1 for reaction, and after the reaction is finished, the two-dimensional non-lead perovskite material (C) is obtained by rapid cooling 18 H 35 NH 3 ) 2 Sn(Cl x1 Br 1-x1 ) 4 。
Preferably, the mixed solution of hydrochloric acid and hydroiodic acid is added into the mixed solution 1 for reaction, and the two-dimensional non-lead perovskite material (C) is obtained by quick cooling after the reaction is finished 18 H 35 NH 3 ) 2 Sn(Cl x2 I 1-x2 ) 4 。
Preferably, hydrogen is addedAdding the mixed solution of iodic acid and hydrobromic acid into the mixed solution 1 for reaction, and quickly cooling after the reaction is finished to obtain the two-dimensional non-lead perovskite material (C) 18 H 35 NH 3 ) 2 Sn(Br x3 I 1-x3 ) 4 。
According to an embodiment of the present invention, the temperature of the mixed solution 1 reacted with the halogen source in the step 2) is 150 to 250 ℃, preferably 160 to 220 ℃, for example, 200 ℃.
Wherein, because the volume amount of the halogen source is small, the temperature of the halogen source added into the mixed solution 1 quickly reaches the same temperature as the mixed solution 1, and therefore, the temperature of the reaction in the step 2) is the same as the temperature of the mixed solution 1.
Preferably, the time for reacting the halogen source with the mixed solution 1 in the step 2) is 5 to 100 seconds, for example, 10 to 60 seconds.
According to an embodiment of the invention, said step 2) is carried out under an inert atmosphere and under stirring.
Preferably, the rapid cooling comprises cooling the reacted solution to room temperature in an ice water bath.
According to an embodiment of the present invention, the step 2) further comprises a step of separating and purifying the reaction product after moderate cooling, and preferably, the separation is performed under a centrifugal condition.
As an embodiment, the step 2) includes the steps of: and (3) heating the mixed solution 1 to 180-250 ℃, adding a halogen source, reacting for 5-60 seconds under an inert atmosphere and a stirring state, cooling the reaction solution to room temperature in an ice water bath, and performing centrifugal separation and purification to obtain the two-dimensional non-lead perovskite material.
The invention also provides the application of the two-dimensional non-lead perovskite material in luminescent display and photoelectronic devices.
The present invention also provides the above (C) 18 H 35 NH 3 ) 2 SnBr 4 The two-dimensional non-lead perovskite material is applied to the fields of luminous display and photoelectronic devices, and is preferably used as an active luminous layer of a white light emitting device.
The present invention also provides a composition comprising (C) above 18 H 35 NH 3 ) 2 SnBr 4 Two-dimensional non-lead perovskite material optoelectronic devices; preferably, the optoelectronic device is a white light emitting device.
Advantageous effects
The invention provides a two-dimensional non-lead perovskite luminescent material which comprises the following components in parts by weight: (C) 18 H 35 NH 3 ) 2 SnCl 4 、(C 18 H 35 NH 3 ) 2 SnBr 4 、(C 18 H 35 NH 3 ) 2 SnI 4 、(C 18 H 35 NH 3 ) 2 Sn(Cl x1 Br 1-x1 ) 4 、(C 18 H 35 NH 3 ) 2 Sn(Cl x2 I 1-x2 ) 4 And (C) 18 H 35 NH 3 ) 2 Sn(Br x3 I 1-x3 ) 4 The two-dimensional halogenated tin perovskite has good luminescence performance, and the organic cations have better protection effect on the photoactive halogenated tin structural unit, so that the two-dimensional halogenated tin perovskite has higher stability than the three-dimensional halogenated tin perovskite.
The two-dimensional non-lead perovskite luminescent material is prepared by adopting a high-temperature hot injection method, the synthesis condition is easy to control, the repeatability is good, and the prepared two-dimensional non-lead perovskite luminescent material has good dispersibility and repeatability; the method effectively regulates and controls the band gap of the two-dimensional non-lead perovskite luminescent material by changing the halogen source, and finally prepares the (C) with different luminescent properties 18 H 35 NH 3 ) 2 SnCl 4 、(C 18 H 35 NH 3 ) 2 SnBr 4 、(C 18 H 35 NH 3 ) 2 SnI 4 、(C 18 H 35 NH 3 ) 2 Sn(Cl x1 Br 1-x1 ) 4 、(C 18 H 35 NH 3 ) 2 Sn(Cl x2 I 1-x2 ) 4 And (C) 18 H 35 NH 3 ) 2 Sn(Br x3 I 1-x3 ) 4 Two-dimensional non-lead perovskite luminescent material. Having orange luminescence(C 18 H 35 NH 3 ) 2 SnBr 4 The luminescent material has good luminescent property, can be used as an active luminescent layer of a white light emitting device, and has great development potential in the fields of luminescent display, optoelectronic devices and the like.
Drawings
FIG. 1 is a low-resolution transmission electron micrograph of a two-dimensional non-lead perovskite luminescent material according to the present invention, wherein (a) is (C) in example 1 18 H 35 NH 3 ) 2 SnCl 4 Low resolution transmission electron micrograph (2 μm on scale), and (b) in example 2 (C) 18 H 35 NH 3 ) 2 SnBr 4 Low resolution transmission electron micrograph (0.5 μm on the scale), and (C) in example 3 (C) 18 H 35 NH 3 ) 2 SnI 4 Low resolution transmission electron microscopy (0.5 μm scale).
FIG. 2 shows (C) in example 1 18 H 35 NH 3 ) 2 SnCl 4 (C) in example 2 18 H 35 NH 3 ) 2 SnBr 4 (C) in example 3 18 H 35 NH 3 ) 2 SnI 4 X-ray powder diffraction pattern of (a).
FIG. 3 shows (C) in example 1 18 H 35 NH 3 ) 2 SnCl 4 (C) in example 2 18 H 35 NH 3 ) 2 SnBr 4 (C) in example 3 18 H 35 NH 3 ) 2 SnI 4 (C) in example 4 18 H 35 NH 3 ) 2 Sn(Cl x1 Br 1-x1 ) 4 (C) in example 5 18 H 35 NH 3 ) 2 Sn(Cl x2 I 1-x2 ) 4 And in example 6 (C) 18 H 35 NH 3 ) 2 Sn(Br x3 I 1-x3 ) 4 Emission spectrum under the excitation of ultraviolet light with different wavelengths.
FIG. 4 shows (C) in example 1 18 H 35 NH 3 ) 2 SnCl 4 (C) in example 2 18 H 35 NH 3 ) 2 SnBr 4 (C) in example 3 18 H 35 NH 3 ) 2 SnI 4 (C) in example 4 18 H 35 NH 3 ) 2 Sn(Cl x1 Br 1-x1 ) 4 (C) in example 5 18 H 35 NH 3 ) 2 Sn(Cl x2 I 1-x2 ) 4 And in example 6 (C) 18 H 35 NH 3 ) 2 Sn(Br x3 I 1-x3 ) 4 Fluorescence lifetime map of material under OPO laser excitation.
Detailed Description
The materials of the present invention, methods of making the same, and uses thereof, are described in further detail below with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
In this example, the following instruments and conditions were used for the test of the compounds:
the model of the low-resolution transmission electron microscope is JEM-2010, and the manufacturer is JEOL.
The X-ray powder diffractometer was MiniFlex2, rigaku manufacturer, and the copper target radiation wavelength was λ =0.154187nm.
The fluorescence spectrometer has an instrument model of FLS980, a manufacturer of Edinburgh, and an excitation light source of a xenon lamp.
The instrument model of the steady-state transient fluorescence phosphorescence spectrometer is FLS980, the manufacturer is Edinburgh, and the excitation light source is an OPO laser.
Example 1
(C 18 H 35 NH 3 ) 2 SnCl 4 Preparation of
Oleylamine, oleic acid and octadecene in a volume ratio of 1Heating stannous to 120 ℃, and stirring to dissolve and react for 1 hour to obtain a mixed solution 1. Heating the mixed solution 1 to 180 ℃, quickly injecting 350 mu L hydrochloric acid, reacting for 60s, placing in an ice water bath, quickly cooling to room temperature, and performing centrifugal separation and purification to obtain (C) 18 H 35 NH 3 ) 2 SnCl 4 And (4) obtaining a product.
Referring to (a) in FIG. 1, the product (C) of this example 18 H 35 NH 3 ) 2 SnCl 4 It has a sheet structure with a size of about 1 μm, and its X-ray powder diffraction pattern is shown in FIG. 2.
As shown in FIG. 3, (C) obtained in this example under 300nm UV excitation 18 H 35 NH 3 ) 2 SnCl 4 The two-dimensional perovskite material exhibits orange light (616 nm) emission.
As can be seen from FIG. 4, (C) obtained in this example 18 H 35 NH 3 ) 2 SnCl 4 τ of the two-dimensional perovskite material was 8.6 μ s (100%).
Example 2
(C 18 H 35 NH 3 ) 2 SnBr 4 Preparation of the Material
Transferring oleylamine, oleic acid and octadecene in a volume ratio of 1. Heating the mixed solution 1 to 200 ℃, quickly injecting 280 mu L hydrobromic acid, reacting for 60s, quickly cooling to room temperature in an ice water bath, and performing centrifugal separation and purification to obtain (C) 18 H 35 NH 3 ) 2 SnBr 4 And (3) obtaining the product.
Referring to (b) in FIG. 1, the product (C) of this example 18 H 35 NH 3 ) 2 SnBr 4 It has a sheet structure with a size of about 1 μm, and its X-ray powder diffraction pattern is shown in FIG. 2.
As shown in FIG. 3, (C) obtained in this example under excitation of 346nm UV light 18 H 35 NH 3 ) 2 SnBr 4 The two-dimensional perovskite material exhibits orange light (619 nm) emission。
As can be seen from FIG. 4, (C) obtained in this example 18 H 35 NH 3 ) 2 SnBr 4 τ of the two-dimensional perovskite material was 4.0 μ s (100%).
Example 3
(C 18 H 35 NH 3 ) 2 SnI 4 Preparation of the Material
Transferring oleylamine, oleic acid and octadecene in a volume ratio of 1. Heating the mixed solution 1 to 200 ℃, quickly injecting 300 mu L hydriodic acid, reacting for 60s, placing in an ice water bath, quickly cooling to room temperature, and performing centrifugal separation and purification to obtain (C) 18 H 35 NH 3 ) 2 SnI 4 And (3) obtaining the product.
As shown in (C) in FIG. 1, the product (C) of this example 18 H 35 NH 3 ) 2 SnI 4 It is in the form of flake with a size of about 1 μm, and its X-ray powder diffraction pattern is shown in FIG. 2.
As shown in FIG. 3, this example yielded (C) under 365nm UV excitation 18 H 35 NH 3 ) 2 SnI 4 The two-dimensional perovskite material exhibits red (666 nm) emission.
As can be seen from FIG. 4, (C) obtained in this example 18 H 35 NH 3 ) 2 SnI 4 τ of the two-dimensional perovskite material was 1.2 μ s (100%).
Example 4
(C 18 H 35 NH 3 ) 2 Sn(Cl x1 Br 1-x1 ) 4 Preparation of the Material
Transferring oleylamine, oleic acid and octadecene in a volume ratio of 1. Heating the mixed solution 1 to 200 ℃, quickly injecting 175 mu L hydrochloric acid and 140 mu L hydrobromic acid, reacting for 60s, placing in an ice water bath, quickly cooling to room temperature,centrifugally separating and purifying to obtain (C) 18 H 35 NH 3 ) 2 Sn(Cl x1 Br 1-x1 ) 4 Product, in halogen feed ratio, x1=0.62.
As shown in FIG. 3, (C) obtained in this example under 341nm UV excitation 18 H 35 NH 3 ) 2 Sn(Cl x1 Br 1-x1 ) 4 The two-dimensional perovskite material exhibits orange light (624 nm) emission.
As can be seen from FIG. 4, (C) obtained in this example 18 H 35 NH 3 ) 2 Sn(Cl x1 Br 1-x1 ) 4 τ of the two-dimensional perovskite material was 4.3 μ s (100%).
Example 5
(C 18 H 35 NH 3 ) 2 Sn(Cl x2 I 1-x2 ) 4 Preparation of the Material
Transferring oleylamine, oleic acid and octadecene in a volume ratio of 1. Heating the mixed solution 1 to 200 ℃, quickly injecting 175 mu L hydrochloric acid and 150 mu L hydriodic acid, reacting for 60s, placing in an ice water bath, quickly cooling to room temperature, and performing centrifugal separation and purification to obtain (C) 18 H 35 NH 3 ) 2 Sn(Cl x2 I 1-x2 ) 4 Product, by halogen feed ratio, x2=0.61.
As shown in FIG. 3, (C) obtained in this example under 365nm UV excitation 18 H 35 NH 3 ) 2 Sn(Cl x2 I 1-x2 ) 4 The two-dimensional perovskite material exhibits red (666 nm) emission.
As can be seen from FIG. 4, (C) obtained in this example 18 H 35 NH 3 ) 2 Sn(Cl x2 I 1-x2 ) 4 τ of the two-dimensional perovskite material was 1.2 μ s (100%).
Example 6
(C 18 H 35 NH 3 ) 2 Sn(Br x3 I 1-x3 ) 4 Preparation of the Material
Transferring oleylamine, oleic acid and octadecene in a volume ratio of 1. Heating the mixed solution 1 to 200 ℃, quickly injecting 140 mu L hydrobromic acid and 150 mu L hydroiodic acid, reacting for 60s, quickly cooling the reaction solution to room temperature in an ice water bath, and performing centrifugal separation and purification to obtain (C) 18 H 35 NH 3 ) 2 Sn(Br x3 I 1-x3 ) 4 Product, by halogen feed ratio, x3=0.49.
As shown in FIG. 3, (C) obtained in this example under 317nm UV excitation 18 H 35 NH 3 ) 2 Sn(Br x3 I 1-x3 ) 4 The two-dimensional perovskite material exhibits orange light (642 nm) emission.
As can be seen from FIG. 4, (C) obtained in this example 18 H 35 NH 3 ) 2 Sn(Br x3 I 1-x3 ) 4 τ of the two-dimensional perovskite material was 0.8 μ s (100%).
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A two-dimensional non-lead perovskite material is characterized in that the molecular formula of the two-dimensional non-lead perovskite material is (C) 18 H 35 NH 3 ) 2 SnX 4 Wherein, X is a halogen element and is selected from one, two or three of Cl, br and I.
2. The two-dimensional non-lead perovskite material of claim 1, wherein (C) is 18 H 35 NH 3 ) 2 SnX 4 Is (C) 18 H 35 NH 3 ) 2 SnCl 4 、(C 18 H 35 NH 3 ) 2 SnBr 4 、(C 18 H 35 NH 3 ) 2 SnI 4 、(C 18 H 35 NH 3 ) 2 Sn(Cl x1 Br 1-x1 ) 4 、(C 18 H 35 NH 3 ) 2 Sn(Cl x2 I 1-x2 ) 4 Or (C) 18 H 35 NH 3 ) 2 Sn(Br x3 I 1-x3 ) 4 And x1, x2, x3 are independently selected from 1, 2 or 3.
Preferably, the two-dimensional non-lead perovskite material is a sheet structure;
preferably, the two-dimensional non-lead perovskite material has an electron microscope topography as shown in fig. 1.
Preferably, the two-dimensional non-lead perovskite material has an XRD pattern as shown in fig. 2.
Preferably, the two-dimensional non-lead perovskite material has orange light or red light emission as shown in figure 3 under the irradiation of the excitation light with the wavelength of 300-365 nm.
Preferably, the two-dimensional non-lead perovskite material has a single-exponential fluorescence decay lifetime as shown in fig. 4.
Preferably, the two-dimensional non-lead perovskite material has a fluorescence quantum yield of 1-90%, preferably 60-90%.
3. A method for producing the two-dimensional non-lead perovskite material as claimed in claim 1 or 2, comprising the steps of:
1) Mixing a tin source, organic amine, organic acid and octadecene to obtain a mixed solution 1;
2) And adding a halogen source into the mixed solution 1 for reaction to obtain the two-dimensional non-lead perovskite material.
4. The method for preparing a two-dimensional non-lead perovskite material as claimed in claim 3, wherein the method further comprises a step of rapid cooling after the halogen source reacts with the mixed solution 1 in the step 2);
preferably, in the step 2), the common concentration of the tin source, the halogen source and the organic amine is not more than 25mol%.
5. The method for preparing a two-dimensional non-lead perovskite material as claimed in claim 3 or 4, wherein the tin source is one, two or more selected from stannous oxalate, stannous octoate, stannous oxide, stannic acetate and dibutyltin.
Preferably, the organic amine is R 1 NH 2 Wherein, said R 1 Is selected from C 4-22 Linear or branched alkyl.
Preferably, the organic acid is R 2 COOH, wherein, the R 2 Is selected from C 6-20 Linear or branched alkyl.
Preferably, the halogen source is selected from one, two or three of hydrochloric acid, hydrobromic acid and hydroiodic acid.
6. The method for producing a two-dimensional non-lead perovskite material as claimed in any one of claims 3 to 5, wherein the mixing in the step 1) is carried out under an inert atmosphere and heating;
preferably, the temperature of mixing in step 1) is 80-200 ℃.
Preferably, the mixing time after heating is 0.5 to 1.5 hours.
7. The method for producing a two-dimensional non-lead perovskite material as claimed in any one of claims 3 to 6, wherein the step 2 comprises the steps of: and adding a halogen source into the mixed solution 1, reacting completely, and then quickly cooling to obtain the two-dimensional non-lead perovskite material.
8. The method for producing a two-dimensional non-lead perovskite material as claimed in any one of claims 3 to 7, wherein the temperature of the mixed solution 1 reacted with the halogen source in the step 2) is 150 to 250 ℃.
Preferably, the time for reacting the halogen source with the mixed solution 1 in the step 2) is 5 to 100 seconds.
Preferably, the rapid cooling comprises cooling the reacted solution to room temperature in an ice water bath.
9. Use of the two-dimensional non-lead perovskite material of claim 1 or 2 in luminescent displays, optoelectronic devices.
Preferably, the two-dimensional non-lead perovskite material is used as an active light emitting layer of a white light emitting device.
10. An optoelectronic device comprising the two-dimensional non-lead perovskite material of claim 1 or 2, preferably the optoelectronic device is a white light emitting device.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104662625A (en) * | 2012-05-18 | 2015-05-27 | 埃西斯创新有限公司 | Optoelectronic devices with organometal perovskites with mixed anions |
| CN108373483A (en) * | 2018-02-22 | 2018-08-07 | 河海大学 | Tin based perovskites and preparation method thereof, solar cell |
| CN109461820A (en) * | 2018-10-25 | 2019-03-12 | 天津理工大学 | Two-dimensional lead-free organic-inorganic hybrid perovskite diode photodetector and preparation method thereof |
| CN111416045A (en) * | 2019-01-07 | 2020-07-14 | 南京工业大学 | Preparation method of non-lead perovskite material, material and device |
| CN111909696A (en) * | 2020-06-24 | 2020-11-10 | 华南理工大学 | Organic-inorganic hybrid zero-dimensional non-lead perovskite material and synthetic method thereof |
-
2021
- 2021-08-23 CN CN202110978054.5A patent/CN115710495A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104662625A (en) * | 2012-05-18 | 2015-05-27 | 埃西斯创新有限公司 | Optoelectronic devices with organometal perovskites with mixed anions |
| CN108373483A (en) * | 2018-02-22 | 2018-08-07 | 河海大学 | Tin based perovskites and preparation method thereof, solar cell |
| CN109461820A (en) * | 2018-10-25 | 2019-03-12 | 天津理工大学 | Two-dimensional lead-free organic-inorganic hybrid perovskite diode photodetector and preparation method thereof |
| CN111416045A (en) * | 2019-01-07 | 2020-07-14 | 南京工业大学 | Preparation method of non-lead perovskite material, material and device |
| CN111909696A (en) * | 2020-06-24 | 2020-11-10 | 华南理工大学 | Organic-inorganic hybrid zero-dimensional non-lead perovskite material and synthetic method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LU HOU: "Tuning Optical Properties of Lead-Free 2D Tin-Based Perovskites with Carbon Chain Spacers", 《THE JOURNAL OF PHYSICAL CHEMISTRY》, vol. 123, no. 51, 4 December 2019 (2019-12-04), pages 31279 - 31285 * |
| XIANGTONG ZHANG: "Bright Orange Electroluminescence fromLead-Free Two-Dimensional Perovskites", 《ACS ENERGY LETTERS》, vol. 4, no. 1, 11 December 2018 (2018-12-11), pages 242 - 248 * |
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