CN114276289A - Two-dimensional single-layer DJ type lead-bromine hybrid perovskite and preparation method and application thereof - Google Patents
Two-dimensional single-layer DJ type lead-bromine hybrid perovskite and preparation method and application thereof Download PDFInfo
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- CN114276289A CN114276289A CN202111600218.7A CN202111600218A CN114276289A CN 114276289 A CN114276289 A CN 114276289A CN 202111600218 A CN202111600218 A CN 202111600218A CN 114276289 A CN114276289 A CN 114276289A
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- 239000002356 single layer Substances 0.000 title claims abstract description 21
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 238000001514 detection method Methods 0.000 claims abstract description 20
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 3
- RHPBLLCTOLJFPH-UHFFFAOYSA-N piperidin-2-ylmethanamine Chemical compound NCC1CCCCN1 RHPBLLCTOLJFPH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002178 crystalline material Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- HBRQLWCXJABKBQ-UHFFFAOYSA-J tetrabromoplumbane Chemical compound Br[Pb](Br)(Br)Br HBRQLWCXJABKBQ-UHFFFAOYSA-J 0.000 claims description 2
- 230000010287 polarization Effects 0.000 abstract description 10
- 150000001412 amines Chemical class 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract description 2
- -1 cyclic amine Chemical class 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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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Abstract
The invention discloses a two-dimensional single-layer DJ type lead-bromine hybrid perovskite constructed by cyclic amine and a preparation method thereof, belonging to the technical field of photoelectric detection. Aiming at the problems of poor stability of the hybrid perovskite material constructed by chain amine and low polarization detection efficiency of the two-dimensional hybrid perovskite material, the two-dimensional single-layer DJ type lead-bromine hybrid perovskite material disclosed by the invention is prepared by a solution method, has a simple preparation process, can be synthesized at a low temperature, is easy to form a film, and has the advantages of better performance and lower cost when used for photovoltaic materials and photoelectric devices. The crystal material has obvious absorption anisotropy, and meanwhile, the DJ structure is favorable for the transmission and separation of current carriers in a system, and the crystal material is an excellent material used in the field of polarized photoelectric detection. The crystal material of the invention greatly improves the stability (to humidity, light and heat) of the prior material (hybrid perovskite constructed by chain amine) by utilizing the fact that no Van der Waals gap exists between DJ type hybrid perovskite layers.
Description
Technical Field
The invention belongs to the technical field of photoelectric detection, and particularly relates to a two-dimensional single-layer DJ type lead-bromine hybrid perovskite, and a preparation method and application thereof.
Background
The polarization detection technology has wide application prospect in the fields of military, civil use and medicine as a novel detection technology and an important detection means. The polarization detection technology has high requirements on the used polarization detection material, and not only has excellent light absorption capacity, but also needs the material to have an asymmetric form or an asymmetric crystal structure. Two-dimensional organic-inorganic hybrid perovskites are a class of emerging low-dimensional semiconductor materials, and are excellent candidate materials for polarization detection due to unique structural anisotropy and chemical diversity. In consideration of practical application, the high detection performance and excellent stability make two important indexes which are simultaneously required to be pursued. In a two-dimensional hybrid perovskite system, attention is paid to DJ-type perovskites which have superior carrier transport performance and higher stability compared with RP-type perovskites. Therefore, the development of high quality, high stability DJ hybrid perovskites offers the possibility of using such materials for the detection of polarized light.
Aiming at the problems of poor stability (to humidity, light and heat) of the conventional material (chain amine constructed hybrid perovskite) and low polarization detection efficiency of a two-dimensional hybrid perovskite material, the invention provides a two-dimensional single-layer DJ type lead-bromine hybrid perovskite constructed by cyclic amine, a preparation method and application in the field of polarization detection.
Disclosure of Invention
Aiming at the problem of poor stability of the hybrid perovskite material constructed by the existing chain amine, the invention provides a two-dimensional single-layer DJ type lead-bromine hybrid perovskite and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the two-dimensional single-layer DJ type lead-bromine hybrid perovskite material is (2-aminomethyl piperidine) PbBr4A crystalline material having the formula: c6H16N2PbBr4The structure is simple as follows: (2AMP) PbBr4；(2AMP)PbBr4The crystal material belongs to an orthorhombic system, a Pbcn space group; (2AMP) PbBr4The crystal material has a unit cell parameter of
Z is 8, unit cell volume
A preparation method of a two-dimensional single-layer DJ type lead-bromine hybrid perovskite material comprises the following steps:
step 1, adding Pb (AC)2·3H2Dissolving O in HBr solution, and adding 2-aminomethyl piperidine to obtain light yellow precipitate;
step 2, heating the light yellow precipitate obtained in the step 1 to boiling to obtain a clear yellow solution, and slowly cooling the solution to room temperature by adopting a gradual cooling method to grow a large-size monocrystal, namely (2AMP) PbBr4A crystalline material.
Further, Pb (AC) in the step 12·3H2The concentration of O was 0.379g/mmol, the concentration of 2-aminomethylpiperidine was 0.12g/mmol, and the concentration of the HBr solution was 48% in HBr solution.
Further, Pb (AC) in the step 12·3H2The dosage of O is 4-5 mmol, the dosage of HBr solution is 10-15 mL, and the dosage of 2-aminomethyl piperidine is 8-9 mmol.
Further, in the step 1, 2-aminomethylpiperidine is reacted with Pb (AC)2·3H2The mass ratio of O is 1: 0.54.
Further, the time for slow cooling by the gradual cooling method in the step 2 is 15-30 days.
The two-dimensional single-layer DJ type lead-bromine hybrid perovskite material has obvious absorption anisotropy and is used for efficient polarized light detection.
Compared with the prior art, the invention has the following advantages:
1. the two-dimensional single-layer DJ type lead-bromine hybrid perovskite material disclosed by the invention is prepared by a solution method, the preparation process is simple, the material can be synthesized at low temperature, and meanwhile, the film is easy to form, and the material has the advantages of better performance and lower cost when being used for photovoltaic materials and photoelectric devices.
2. The crystal material has obvious absorption anisotropy, and meanwhile, the DJ structure is favorable for the transmission and separation of current carriers in a system, and the crystal material is an excellent material used in the field of polarized photoelectric detection.
3. The crystal material of the invention greatly improves the stability (to humidity, light and heat) of the prior material (hybrid perovskite constructed by chain amine) by utilizing the fact that no Van der Waals gap exists between DJ type hybrid perovskite layers.
Drawings
FIG. 1 shows (2AMP) PbBr4Schematic of the bulk crystal of (a);
FIG. 2 shows (2AMP) PbBr4The structural schematic diagram of the DJ type two-dimensional lead-bromine single-layer hybrid perovskite;
FIG. 3 shows (2AMP) PbBr4A band gap diagram;
FIG. 4 shows (2AMP) PbBr4Polar axis diagram of current-light polarization angle of the device under dark state and 405nm polarized illumination;
FIG. 5 shows (2AMP) PbBr4Device rise and fall optical response times.
Detailed Description
Example 1
Pb (AC)2·3H2O (4mmol) was dissolved in 10mL (48 wt.%) of HBr solution. Subsequently, 8mmol of 2-aminomethylpiperidine was added to the solution to obtain a pale yellow precipitate. After heating to boiling, a clear, pale yellow solution was obtained. The solution is gradually cooled from 70 deg.C to 25 deg.C at a rate of 1 deg.C per day, and after 25 days, (2AMP) PbBr is obtained4And (4) large-size single crystals. The crystal structure was analyzed by an X-ray single crystal diffractometer as shown in fig. 2.
Example 2
(2AMP)PbBr4Absorption capacity analysis of crystalline materials:
pairing of synthetic organic-inorganic hybrid (2AMP) PbBr by ultraviolet-visible (UV-Vis) absorption Spectroscopy4The absorption property analysis of the crystal material shows that the absorption cut-off edge of the crystal can reach 430nm (figure 3), and the direct bandGap, (E)g) Is 2.9 eV.
Example 3
(2AMP)PbBr4The polarized photoelectric detection performance of the crystal material under the irradiation of 405nm polarized light is analyzed:
in the dark state without light, (2AMP) PbBr4Dark current of single crystal device is as low as 4.75 x 10-11A(Vbias10V), indicating that the intrinsic carrier concentration of the compound is low, reflecting the high quality of the crystalline material. Furthermore, (2AMP) PbBr was investigated under 405nm polarized light4Photocurrent and photoresponse curves of the single crystal devices. With (2AMP) PbBr4The on-off ratio of the constructed device can reach 10 under polarized light of 405nm2The polarization ratio can reach 1.23. This result is also sufficient to show that the crystal is an excellent polarized photodetection material.
Example 4
Pb (AC)2·3H2O (5mmol) was dissolved in 15mL (48 wt.%) of HBr solution. Subsequently, 9mmol of 2-aminomethylpiperidine was added to the solution to obtain a yellow precipitate. After heating to boiling, a clear, pale yellow solution was obtained. The solution is gradually cooled from 75 ℃ to 25 ℃ at a rate of 0.5 ℃ per day, and after 30 days, (2AMP) PbBr can be grown at room temperature4And (4) large-size single crystals. The crystal structure was analyzed by an X-ray single crystal diffractometer as shown in fig. 2.
The performance evaluation of the invention:
(1) light absorption property
(2AMP)PbBr4The crystal is light yellow, and an ultraviolet-visible absorption spectrogram of the material shows that the crystal has strong absorption in ultraviolet and visible light regions, the absorption cut-off edge can reach 430nm (figure 3), and the crystal is calculated to be a direct band gap semiconductor and has a band gap (E)g) 2.9eV, indicating that the crystal is a promising candidate material for optical detection.
(2)405nm polarized photoelectric detection performance
To test the photodetection performance of the crystalline material, we assembled a small photodetector. Based on (2AMP) PbBr4Two-dimensional single-layer DJ type hasThe organic-inorganic hybrid perovskite photoelectric detector has lower dark current (10)-11A) Larger on-off ratio (10) under 405nm polarized illumination2). Furthermore, the rise/fall time (τ r/τ f) of the device is about 224/310 μ s. While the material exhibits a large polarization ratio (1.23) due to absorption anisotropy.
Those skilled in the art will appreciate that the invention may be practiced without these specific details. Although illustrative embodiments of the present invention have been described above to facilitate the understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all matters of the invention which utilize the inventive concepts are protected.
Claims (7)
1. A two-dimensional monolayer DJ type lead-bromine hybrid perovskite material is characterized in that: the two-dimensional single-layer DJ type lead-bromine hybrid perovskite material is (2-aminomethyl piperidine) PbBr4A crystalline material having the formula: c6H16N2PbBr4The structure is simple as follows: (2AMP) PbBr4；(2AMP)PbBr4The crystal material belongs to an orthorhombic system, a Pbcn space group; (2AMP) PbBr4The crystal material has a unit cell parameter of
Z is 8, unit cell volume
2. The preparation method of the two-dimensional monolayer DJ type lead-bromine hybrid perovskite material as claimed in claim 1, which is characterized in that: the method comprises the following steps:
step 1, adding Pb (AC)2·3H2Dissolving O in HBr solution, and adding 2-aminomethyl piperidine to obtain light yellow precipitate;
step 2, heating the light yellow precipitate obtained in the step 1 to boiling to obtain a clear yellow solution, and slowly cooling the solution to room temperature by adopting a gradual cooling method to grow a large-size monocrystal, namely (2AMP) PbBr4A crystalline material.
3. The preparation method of the two-dimensional double-layer DJ type lead-bromine hybrid perovskite material as claimed in claim 2, wherein the preparation method comprises the following steps: pb (AC) in said step 12·3H2The concentration of O was 0.379g/mmol, the concentration of 2-aminomethylpiperidine was 0.12g/mmol, and the concentration of the HBr solution was 48% in HBr solution.
4. The preparation method of the two-dimensional monolayer DJ type lead-bromine hybrid perovskite material as claimed in claim 2, wherein the preparation method comprises the following steps: pb (AC) in said step 12·3H2The dosage of O is 4-5 mmol, the dosage of HBr solution is 10-15 mL, and the dosage of 2-aminomethyl piperidine is 8-9 mmol.
5. The preparation method of the two-dimensional monolayer DJ type lead-bromine hybrid perovskite material as claimed in claim 2, wherein the preparation method comprises the following steps: the 2-aminomethylpiperidine with Pb (AC) in the step 12·3H2The mass ratio of O is 1: 0.54.
6. The preparation method of the two-dimensional monolayer DJ type lead-bromine hybrid perovskite material as claimed in claim 2, wherein the preparation method comprises the following steps: and (3) slowly cooling for 15-30 days by using a gradual cooling method in the step (2).
7. The application of the two-dimensional single-layer DJ type lead-bromine hybrid perovskite material is characterized in that: the obtained two-dimensional single-layer crystal material has obvious absorption anisotropy and is used for efficient polarized light detection.
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| CN113437226A (en) * | 2021-05-19 | 2021-09-24 | 华北电力大学 | Preparation method of 4-pyridylmethylamine bromine optimized tin-lead mixed perovskite solar cell |
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