CN112575373A - Cs2AgBiBr6Rb-doped single crystal and synthesis and application thereof - Google Patents
Cs2AgBiBr6Rb-doped single crystal and synthesis and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 65
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- JAAGVIUFBAHDMA-UHFFFAOYSA-M rubidium bromide Chemical compound [Br-].[Rb+] JAAGVIUFBAHDMA-UHFFFAOYSA-M 0.000 claims description 34
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 30
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
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- 238000009792 diffusion process Methods 0.000 abstract description 18
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- 238000004020 luminiscence type Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 17
- 230000005284 excitation Effects 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a lead-free perovskite Cs2AgBiBr6A method for synthesizing doped Rb belongs to the field of material luminescence. The method comprises the following steps: in the synthesis of lead-free perovskite Cs2AgBiBr6In the process, Rb with different contents is adopted to lead-free perovskite Cs2AgBiBr6And (6) doping. The invention realizes the lead-free perovskite Cs2AgBiBr6And growing the Rb doped single crystal. By doping with different Rb contents, lead-free perovskite Cs2AgBiBr6The fluorescence intensity of the lead-free perovskite Cs is increased and then reduced2AgBiBr6Has a first increased life and a second decreased life, and is free of lead2AgBiBr6The diffusion coefficient of (A) is increased and then reduced to lead-free perovskite Cs2AgBiBr6ProvideGuiding significance.
Description
Technical Field
The invention belongs to the field of luminescent materials, and particularly relates to lead-free perovskite Cs2AgBiBr6Synthesis of Rb-doped single crystalsMethod
Background
In recent years, a novel semiconductor material-organic-inorganic hybrid perovskite ABX3[A＝CH3NH3+,(H2N)2CH+；B＝Pb2+；X＝Cl-,Br-or I-]Has received wide attention from scientists. The Miyasaka team first applied MAPbI to solar cells in 20093At the beginning, research on perovskite cells has started to generate a hot trend, the photoelectric conversion efficiency of perovskite solar cells has risen from 3.8% at the beginning to more than 22% at present, and the service life of perovskite solar cells has increased thousands of hours from the first few hours. The organic-inorganic hybrid perovskite is selected by science in 2013 as one of ten scientific breakthroughs in the world, and the scientists point out that the future scientists will concentrate on researching the peculiar material called perovskite in 2016 nature
However, conventional organic-inorganic hybrid perovskite ABX3[A＝CH3NH3+,(H2N)2CH+；B＝Pb2+；X＝Cl-,Br-or I-]Most of the lead-containing perovskite contains lead element, which causes certain toxicity of perovskite and is greatly limited in application. In order to solve the problem of perovskite toxicity, scientists propose a novel lead-free perovskite with a molecular structural formula A2BB’X6The divalent toxic metal element, lead, is replaced at the B site by a combination of a monovalent metal and a trivalent metal. The advent of this new lead-free perovskite has greatly reduced the toxicity problems of conventional perovskites, and has opened the possibility to expand the perovskite applications. However, the research on the novel lead-free perovskite is still in the preliminary stage, the lead-free perovskite has a more complex crystal structure, and the photoelectric properties of the lead-free perovskite researched are poor. To this end, the present invention proposes a doping mechanism by doping lead-free perovskite Cs with a metal element Rb2AgBiBr6Effectively improves the lead-free perovskite Cs2AgBiBr6Photoelectric properties of (1) is thatBetter application to photoelectric materials provides a guiding idea.
Disclosure of Invention
In order to better research the lead-free perovskite Cs2AgBiBr6To increase the awareness and understanding of the lead-free perovskite Cs, the invention is primarily directed to2AgBiBr6A method for synthesizing a doped Rb single crystal. Improvement of lead-free perovskite Cs by doping of different contents of metal element Rb2AgBiBr6The photoelectric properties of (1).
The invention mainly adopts the following implementation scheme: firstly, raw materials CsBr and BiBr are adopted3Heating, stirring and dissolving, and then adding AgBr and RbBr in a certain ratio until the AgBr and the RbBr are dissolved. Keeping the temperature for a certain time, cooling to room temperature at a certain rate, standing overnight, repeatedly washing with anhydrous isopropanol the next day until the washing liquid is colorless, and oven drying to obtain Cs2AgBiBr6、Cs2AgBiBr6-0.1Rb、Cs2AgBiBr6-0.2Rb、Cs2AgBiBr6-0.3Rb single crystal. And respectively taking out parts of the single crystals of the doped samples with different Rb contents, grinding the parts by using an agate mortar, sealing and filling the parts into a small bottle. Mixing the ground Cs with different Rb contents2AgBiBr6And (6) carrying out XRD test on the sample. Mixing the ground Cs with different Rb contents2AgBiBr6The sample was tested for absorption. The method is characterized in that a fluorescence scanning confocal microscopic imaging system which is built by a laboratory is excited in a wide field to measure Cs with different doping contents Rb under the same energy2AgBiBr6Fluorescence and lifetime of the sample. Under the condition of lower energy, the single-point excitation is carried out to collect the Cs doped with different Rb contents2AgBiBr6Fluorescence imaging of the sample. And (4) normalizing the light spots at other moments by taking the fluorescence intensity at the moment 0 as a reference. Extracting Cs doped with different Rb contents at different times2AgBiBr6One-dimensional fluorescence intensity distribution of fluorescence intensity of the sample is obtained by adopting Gaussian fitting fluorescence intensity to obtain standard deviation of fluorescence intensity, and a fluorescence intensity standard deviation curve at different moments is made, wherein the slope of the curve is the slope of the fluorescence intensity standard deviation curve, namely the Cs doped with different Rb contents2AgBiBr6Diffusion coefficient of the sample.
The object of the present invention is achieved by the following means.
Lead-free perovskite Cs2AgBiBr6The synthesis method of the doped Rb monocrystal comprises the following specific steps:
(1) lead-free perovskite Cs2AgBiBr6Preparation of single crystal: a crystallization method is adopted. Firstly, raw materials CsBr and BiBr are adopted3Heating to 130 ℃, stirring to dissolve, and then adding AgBr until dissolving. Keeping the temperature for several hours, cooling to room temperature at the rate of 10 ℃ per hour, standing overnight, repeatedly washing with anhydrous isopropanol the next day until the washing liquid is colorless, and drying at 60 ℃ to obtain Cs2AgBiBr6And (3) single crystal.
(2) Lead-free perovskite Cs2AgBiBr6Preparation of Rb doped single crystal: a crystallization method is adopted. Firstly, raw materials CsBr and BiBr are adopted3Heating, stirring and dissolving, and then adding AgBr and RbBr in a certain proportion until the AgBr and the RbBr are dissolved. Keeping the temperature for a certain time, cooling to room temperature at a certain speed, standing overnight, repeatedly washing with anhydrous isopropanol the next day until the washing liquid is colorless, and drying to obtain CsBr and BiBr3Heating, stirring and dissolving, and then adding AgBr until dissolving. Keeping the temperature for a certain time, cooling to room temperature at a certain rate, standing overnight, repeatedly washing with anhydrous isopropanol the next day until the washing liquid is colorless, and oven drying to obtain Cs2AgBiBr6Doping Rb single crystal.
Synthetic Cs2AgBiBr6-0.1Rb single crystal is prepared from the following raw materials: 2mmol CsBr, 1mmol AgBr, 0.1mmol RbBr, 1mmol BiBr3(ii) a Synthetic Cs2AgBiBr6-0.2Rb single crystal is prepared from the following raw materials: 2mmol CsBr, 1mmol AgBr, 0.2mmol RbBr, 1mmol BiBr3(ii) a Synthetic Cs2AgBiBr6-0.3Rb single crystal is prepared from the following raw materials: 2mmol CsBr, 1mmol AgBr, 0.3mmol RbBr, 1mmol BiBr3。
(3) Lead-free perovskite Cs2AgBiBr6Doping Rb single crystal XRD test: the samples doped with different Rb contents were ground and sealed into powders, which were subjected to XRD testing, XRD testing on a common test platform of the institute of Union, Chinese academy of sciences.
The instrument used is an X-ray powder diffractometer (XRD), the model is Empyrean-100, the scanning angle is 10-80 degrees, and the scanning speed is 8 degrees/min.
(4) Testing lead-free perovskite Cs2AgBiBr6And lead-free perovskite Cs2AgBiBr6Rb-doped single crystal absorption test: the synthesized lead-free perovskite Cs2AgBiBr6And the samples doped with different Rb contents were ground into powders and subjected to absorption test using an ultraviolet-visible spectrophotometer.
The instrument used was an ultraviolet visible spectrophotometer model Agilent Cary 60.
(5) Lead-free perovskite Cs2AgBiBr6And lead-free perovskite Cs2AgBiBr6Fluorescence test of doped Rb Single Crystal: and (3) wide field excitation, namely excitation with certain energy (lower energy), measuring the fluorescence of the samples doped with different Rb contents, and comparing the fluorescence intensity among samples which cannot be excited.
Measurement of the synthesized lead-free perovskite Cs at the same energy2AgBiBr6And lead-free perovskite Cs2AgBiBr6The fluorescence of the doped Rb single crystal is compared with the relative fluorescence intensity of the single crystals with different Rb contents.
Excitation energy is 0.5uw by adopting wide field excitation.
(6) Lead-free perovskite Cs2AgBiBr6And lead-free perovskite Cs2AgBiBr6Lifetime test of Rb-doped single crystal: and (3) wide field excitation, namely excitation at certain energy (lower energy), measuring the service life of the doped samples with different Rb contents, and comparing the service life of the samples which cannot be subjected to different types of Rb.
Measurement of the synthesized lead-free perovskite Cs at the same energy2AgBiBr6And lead-free perovskite Cs2AgBiBr6The service life of the doped Rb single crystal is compared with the service life of the single crystals with different Rb contents, and the change of the ratio of the fast component and the slow component is obtained by fitting a service life curve.
Excitation energy is 0.5uw by adopting wide field excitation.
(7) Lead-free perovskite Cs2AgBiBr6And lead-free perovskite Cs2AgBiBr6Diffusion coefficient calculation of Rb-doped single crystal: extracting one-dimensional fluorescence intensity of sample doped with different Rb contents at different momentsAnd (3) distribution, adopting Gaussian fitting of fluorescence intensity to obtain the standard deviation of the fluorescence intensity, and making a fluorescence intensity standard deviation curve at different moments, wherein the slope of the curve is the diffusion coefficient of the samples with different Rb doping proportions.
Extracting Cs at different times at room temperature2AgBiBr6And lead-free perovskite Cs2AgBiBr6Adopting Gaussian fitting fluorescence intensity to obtain standard deviation of fluorescence intensity, making standard deviation curve of fluorescence intensity at different times, wherein the slope of the curve is the lead-free perovskite Cs2AgBiBr6And lead-free perovskite Cs2AgBiBr6The diffusion coefficients of the Rb doped samples are compared, and the magnitude of the diffusion coefficients of different samples is compared.
Single point excitation was used with an excitation energy of 0.5 uw.
Preferably, the synthetic raw materials in the step (1) are 1-2mmol CsBr, 0.5-1mmol AgBr and 0.5-1mmol BiBr3. The heating and stirring temperature is 130-150 ℃. The cooling rate is 5-10 ℃/h, and the drying temperature after the single crystal is washed is 40-60 ℃.
Preferably, the synthesis raw materials in the step (2) are 1-2mmol CsBr, 0.5-1mmol AgBr and 0.5-1mmol BiBr30-0.3 mmoleRbBr. The heating and stirring temperature is 130-150 ℃. The cooling rate is 5-10 ℃/h, and the drying temperature after the single crystal is washed is 40-60 ℃.
Preferably, the lead-free perovskite Cs of the step (3)2AgBiBr6The scanning range of the Rb doped single crystal XRD is 10-80 degrees, and the scanning speed is 8-10 degrees/min.
Preferably, the lead-free perovskite Cs of the step (5)2AgBiBr6The excitation energy of the Rb-doped single crystal fluorescence test is the same as the energy collected in the same service life, and the wide field excitation is adopted, and the energy is less than 0.5 uw.
Preferably, the lead-free perovskite Cs of the step (6)2AgBiBr6The energy of the lifetime test of the doped Rb single crystal is less than 0.5uw, and the wide field excitation is realized.
Preferably, step (7) is carried out using lead-free perovskite Cs2AgBiBr6The calculated energy of the diffusion coefficient of the doped Rb single crystal is less than 0.5uw, and the single-point excitation is realized.
Lead-free perovskitesCs2AgBiBr6Diffusion coefficient calculation of Rb-doped single crystal:
at lower energies (energies at the intrinsic lifetime of the crystal), lead-free perovskite Cs2AgBiBr6The fluorescence intensity of the doped Rb monocrystal meets Gaussian distribution at the moments of 0 and t ns, and the fluorescence intensity of 0 and t ns can be expressed in a Gaussian formula as follows:
wherein n (x, y,0) and n (x, y, t) represent the number of carriers at times 0 and t, respectively; sigma2 0,x，σ2 0,y，σ2 t,x，σ2 t,yRepresenting the variation of the two-dimensional gaussian distribution of carriers in the x and y directions at different delay times, respectively.
Only the X-axis direction is selected as a research object, the spot change of the y-axis and the z-axis at any time is 0, and the lead-free perovskite Cs is obtained at the time t2AgBiBr6The standard deviation of the fluorescence intensity of the doped Rb single crystal can be written as follows:
wherein L is the diffusion distance of the carrier, and D is the diffusion coefficient.
After the formula (2) is finished, the formula can be written as follows, and the formula (3) can be used for solving the lead-free perovskite Cs2AgBiBr6Diffusion coefficient of Rb-doped single crystal
The invention realizes the lead-free perovskite Cs2AgBiBr6And growing the Rb doped single crystal. By doping with different Rb contents, lead-free perovskite Cs2AgBiBr6The fluorescence intensity of the lead-free perovskite Cs is increased and then reduced2AgBiBr6Has a first increased life and a second decreased life, and is free of lead2AgBiBr6The diffusion coefficient of (A) is increased and then reduced to lead-free perovskite Cs2AgBiBr6Provides guiding significance for research and development.
Compared with the prior art, the invention has the beneficial effects that:
(1) the lead-free perovskite Cs of the invention2AgBiBr6Rb-doped synthesis method and synthesized lead-free perovskite Cs2AgBiBr6The doped Rb single crystal has regular appearance and less surface defects.
(2) The lead-free perovskite Cs of the invention2AgBiBr6The Rb-doped synthesis method realizes the synthesis of lead-free perovskite Cs2AgBiBr6The band gap of (3) is adjusted.
(3) The lead-free perovskite Cs of the invention2AgBiBr6The single crystal synthesized by the Rb doping synthesis method increases fluorescence first and then decreases along with the increase of the Rb doping amount.
(4) The lead-free perovskite Cs of the invention2AgBiBr6The lifetime of the single crystal synthesized by the Rb-doped synthesis method is increased and then decreased along with the increase of the Rb doping amount.
(5) The lead-free perovskite Cs of the invention2AgBiBr6The diffusion coefficient of the single crystal synthesized by the Rb doping synthesis method is increased firstly and then reduced along with the increase of the Rb doping amount. Is lead-free perovskite Cs2AgBiBr6And guidance is provided for obtaining better optical performance.
Drawings
FIG. 1 shows lead-free perovskite Cs prepared in example 12AgBiBr6Single crystal diagram of doped Rb.
FIG. 2 shows lead-free perovskite Cs prepared in example 12AgBiBr6XRD pattern of Rb doped single crystals.
FIG. 3 shows lead-free perovskite Cs prepared in example 12AgBiBr6Absorption profile of Rb doped single crystal.
FIG. 4 shows lead-free perovskite Cs prepared in example 12AgBiBr6Fluorescence of Rb doped single crystals.
FIG. 5 shows lead-free perovskite Cs prepared in example 12AgBiBr6Lifetime of Rb-doped Single crystals。
FIG. 6 shows lead-free perovskite Cs prepared in example 12AgBiBr6Fluorescence of Rb doped single crystals light intensity distribution along the X axis at 0, 10, 20, 25, 30 ns.
FIG. 7 shows lead-free perovskite Cs prepared in example 12AgBiBr6The single crystal doped with Rb was fitted to the diffusion coefficient and the diffusion coefficient D was calculated.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The reagents used in the examples are all commercially available.
Example 1
Lead-free perovskite Cs2AgBiBr6The synthesis method of the doped Rb specifically comprises the following steps:
(1) CsBr 426mg, BiBr were weighed accurately3448mg of the catalyst is dissolved in 20ml of HBr, stirred and heated at 130 ℃ until the catalyst is dissolved, and AgBr 188mg is added respectively; 188mg of AgBr and 16mg of RbBr; 188mg of AgBr and 32mg of RbBr; 188mg of AgBr and 48mg of RbBr, stirring continuously until the AgBr and the RbBr are dissolved, keeping the temperature for two hours, then cooling to room temperature at the speed of 10 ℃/h, standing overnight, washing a sample with an isopropanol solution until the sample is clear, and drying the sample at the temperature of 60 ℃.
(2) Grinding part of the dried sample, and performing XRD test on a common test platform of the institute of university of Chinese academy of sciences with the instrument model of Empyrean-100, the scanning angle of 10-80 degrees and the scanning speed of 8 degrees/min
(3) Grinding part of dried samples to prepare lead-free perovskite Cs with different Rb doping contents2AgBiBr6The absorption test of (1).
(4) The fluorescence scanning confocal microscopic imaging system which is built by a laboratory automatically tests lead-free perovskite Cs with different Rb doping contents by using a 100X objective, 0.5uw energy image and wide field excitation2AgBiBr6The fluorescence intensity of (2).
(5) The fluorescence scanning confocal microscopic imaging system which is built by a laboratory automatically tests lead-free perovskite Cs with different Rb doping contents by using a 100X objective, 0.5uw energy image and wide field excitation2AgBiBr6The life of (2).
(6) The lead-free perovskite Cs with different Rb doping contents is carried out at normal temperature through a fluorescence scanning confocal microscopic imaging system which is automatically built in a laboratory2AgBiBr6Fluorescence imaging of (2). Extracting lead-free perovskite Cs with different Rb doping contents at 0, 10, 20, 25 and 30ns moments2AgBiBr6The X-axis fluorescence intensity distribution of the fluorescence intensity adopts Gaussian fitting fluorescence intensity to obtain the standard deviation of the fluorescence intensity.
Lead-free perovskite Cs with different Rb doping contents prepared by the embodiment2AgBiBr6The single crystal is shown in FIG. 1. The prepared single crystal has regular appearance. The surface defects are few.
Lead-free perovskite Cs with different Rb doping contents prepared by the embodiment2AgBiBr6XRD of the single crystal is shown in fig. 2. With the increase of the Rb doping amount, the diffraction peak of the single crystal gradually shifts to a small angle.
Lead-free perovskite Cs with different Rb doping contents prepared by the embodiment2AgBiBr6The absorption of the single crystal is shown in figure 3. Lead-free perovskite Cs with different Rb doping contents along with increase of Rb doping amount2AgBiBr6The band gap of the single crystal is gradually enlarged, and the lead-free perovskite Cs is realized2AgBiBr6And regulating and controlling the band gap of the single crystal.
Lead-free perovskite Cs with different Rb doping contents prepared by the embodiment2AgBiBr6The fluorescence of the single crystal is shown in FIG. 4. Lead-free perovskite Cs with different Rb doping contents along with increase of Rb doping amount2AgBiBr6The fluorescence intensity of the single crystal increases first and then decreases.
Lead-free perovskite Cs with different Rb doping contents prepared by the embodiment2AgBiBr6The lifetime of the single crystal is shown in FIG. 5. Lead-free perovskite Cs with different Rb doping contents along with increase of Rb doping amount2AgBiBr6The lifetime of the single crystal is increased and then decreased.
Lead-free perovskite Cs with different Rb doping contents prepared by the embodiment2AgBiBr6The diffusion coefficient fit for the single crystal is shown in fig. 6.
This example systemPrepared lead-free perovskite Cs with different Rb doping contents2AgBiBr6The diffusion coefficient fitting results for the single crystal are shown in fig. 7. Lead-free perovskite Cs with different Rb doping contents along with increase of Rb doping amount2AgBiBr6The diffusion coefficient of the single crystal increases first and then decreases.
Claims (4)
1. Cs (volatile organic Compounds)2AgBiBr6An Rb-doped single crystal characterized by: is in lead-free perovskite Cs2AgBiBr6The single crystal material is doped with Rb, wherein the molar ratio of Rb to Ag in the single crystal material is 0.05-0.4, preferably 0.1-0.3, more preferably 0.15-0.25, and most preferably 0.2.
2. A method for synthesizing a single crystal according to claim 1, comprising the steps of: firstly, raw materials CsBr and BiBr are adopted3Heating, stirring and dissolving, and then adding AgBr and RbBr in required proportion until the AgBr and the RbBr are dissolved; keeping the temperature at 130 ℃ and 150 ℃ for 1-10 hours (preferably 2-5 hours), cooling to room temperature-40 ℃ at the rate of 5-10 ℃ per hour (preferably 8-10 ℃ per hour), standing for 10-24 hours (preferably 10-14 hours), washing with anhydrous isopropanol until the washing liquid is colorless, and drying at 40-60 ℃ to obtain Cs2AgBiBr6Doping Rb single crystal.
3. A synthesis method according to claim 2,
the proportion of the synthetic raw materials is as follows: 1-2mmol CsBr, 0.5-1mmol AgBr,0.5-1mmol BiBr3、0.05-0.4mmol RbBr；
Preferably: 2mmol CsBr, 1mmol AgBr, 1mmol BiBr30.1-0.3mmol RbBr; more preferably: 2mmol CsBr, 1mmol AgBr, 1mmol BiBr30.15-0.25mmol of RbBr; most preferably: 2mmol CsBr, 1mmol AgBr, 1mmol BiBr3、0.2mmol RbBr。
4. The lead-free perovskite Cs of claim 12AgBiBr6Application of the doped Rb single crystal in perovskite solar cells.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910940204.6A CN112575373A (en) | 2019-09-30 | 2019-09-30 | Cs2AgBiBr6Rb-doped single crystal and synthesis and application thereof |
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| CN107934916A (en) * | 2017-11-16 | 2018-04-20 | 中山大学 | It is a kind of to stablize the nanocrystalline preparation methods of unleaded full-inorganic double-perovskite A2BB ' X6 |
| CN108659827A (en) * | 2018-06-15 | 2018-10-16 | 华中科技大学 | Near ultraviolet excitated double-perovskite single-substrate white fluorescent material and preparation and application |
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| CN107934916A (en) * | 2017-11-16 | 2018-04-20 | 中山大学 | It is a kind of to stablize the nanocrystalline preparation methods of unleaded full-inorganic double-perovskite A2BB ' X6 |
| CN108659827A (en) * | 2018-06-15 | 2018-10-16 | 华中科技大学 | Near ultraviolet excitated double-perovskite single-substrate white fluorescent material and preparation and application |
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| ADAM H.SLAVNEY ET AL.: "A Bismuth-Halide Double Perovskite with Long Carrier Recombination Lifetime for Photovaltaic Applications", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
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