CN115710502B - Yb 3+ Doped CsPbBr 3 PMSCs, preparation method and application thereof - Google Patents
Yb 3+ Doped CsPbBr 3 PMSCs, preparation method and application thereof Download PDFInfo
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Abstract
Yb of the present invention 3+ Doped CsPbBr 3 PMSCs, a preparation method and application thereof, and belongs to the technical field of photoelectric material preparation. The preparation method of the invention comprises the following steps: weighing CsBr and PbBr according to a proportion 2 Then dissolving the mixture in a solvent to obtain a mixed solution 1; oleic acid and oleylamine are sequentially added into the mixed solution 1 according to a proportion, and a mixed solution 2 is obtained after dissolution; weighing Yb-containing materials according to a proportion 3+ Adding the compound into the mixed solution 2, and dissolving to obtain a precursor solution; injecting the precursor solution into an antisolvent to obtain Yb 3+ Doped CsPbBr 3 PMSCs solution; high-speed centrifugal washing purified Yb 3+ Doped CsPbBr 3 PMSCs solution. Yb of the present invention 3+ Doped CsPbBr 3 PMSCs have the advantages of high efficiency, double emission, high fluorescence quantum yield and excellent stability, and can be applied to the near infrared light-emitting field and photoelectric devices.
Description
Technical Field
The invention belongs to the technical field of photoelectric material preparation, and particularly relates to Yb 3+ Doped CsPbBr 3 PMSCs, and preparation method and application thereof.
Background
The low-dimensional Perovskite Magic Size Cluster (PMSCs) material has the unique advantages of adjustable luminescent color, excellent charge transmission performance, high purity of narrow-band emission color, obvious light quantum effect and the like, and has great development potential in the fields of bioluminescence imaging, cell marking, ultra-high definition display, biochemical sensors, photocatalysis and the like. However, PMSCs have the defects that the stability and storage performance in the environment are poor, toxic heavy metal lead elements are contained, and the spectrum range can only cover the visible light region due to more surface defects caused by larger specific surface area, and on the basis of the defects, the PMSCs face serious challenges for designing, developing and applying PMSCs-based photoelectric devices in the future.
Structurally and performance, the PMSCs material has the unique properties of small size (-2 nm), narrow fluorescence half-width (FWHM < 15 nm), obvious quantum finite field effect, higher specific surface area and more surface defects, and the like, thus being capable of carrying out structural property on the PMSCs materialCan be modified. Currently, csPbBr is concerned 3 Related studies of PMSCs have focused mainly on the correlation of unique size, composition, stability and optoelectronic properties. By CsPbBr 3 PMSCs are modified to prepare the transition metal Mn with higher fluorescence quantum yield 2+ Doping and small size (-2 nm) samples, but the existing technology of doping PMSCs has not broken through the technical bottleneck of near infrared luminescence.
The lanthanide rare earth ion doped low-dimensional PMSCs material not only has the intrinsic excellent physical and chemical properties of the PMSCs material, but also endows the PMSCs material with excellent optical, electric, magnetic, catalytic and other unique properties, and can create new emission characteristics, enhance stability, reduce defect state density and the like, so that the lanthanide rare earth ion and the PMSCs material can be used for preparing novel photoelectric functional materials with excellent photoelectric properties and stability by the synergistic effect. The study focused CsPbBr 3 PMSCs were studied, csPbBr in composition 3 The structure of PMSCs is composed of Cs + 、Pb 2+ And halogen ions Br - Composition; structurally, lanthanide rare earth ions are generally introduced into A, B or B positions of perovskite to widen CsPbBr 3 The light-emitting spectrum range of PMSCs is from the original ultraviolet light region to the ultraviolet-near infrared light region, so that the photoelectric application range of the material is improved; physically and chemically, csPbBr with quantum confinement effect compared to large-sized perovskite blocks and perovskite thin films 3 The PMSCs material has larger exciton binding energy, and the combination of a surface passivation strategy and a doping substitution strategy can effectively reduce surface defects and effectively improve the stability, toxicity and photoelectric performance of the material. Furthermore, in comparison to organic-inorganic hybrid perovskite, inorganic CsPbBr 3 PMSCs are provided with a temperature, H, due to the absence of organic components 2 O and O 2 Stronger stability. Thus, inorganic CsPbBr 3 The preparation and synthesis process of PMSCs has very broad market prospect for promoting the application in the field of novel photoelectric devices. The lanthanide rare earth ions have extremely rich energy levels and 4f electron transition effects, so that the rare earth doped material has quantum behaviors and photoelectric characteristics with wide spectral range and rich connotation. General purpose medicineOverdoping substitution strategy, csPbBr 3 The PMSCs can realize the absorption and emission of the ultraviolet region and the near infrared region, thereby effectively improving and expanding the photoelectric application of the PMSCs. However, there is no report on the research on lanthanide rare earth doped PMSCs.
Therefore, the lanthanide rare earth ion doped PMSCs has important research significance and practical value for preparing high-quality perovskite type up-conversion nano material devices.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides the Yb with high efficiency, double emission, high fluorescence quantum yield and excellent stability 3+ Doped CsPbBr 3 PMSCs, preparation method and application thereof, and CsPbBr realization method 3 PMSCs stably store in the external environment and stably emit light in a near infrared region, so that CsPbBr with excellent reaction generation stability and optical performance is achieved 3 Target of PMSCs.
To achieve the above object, the present invention provides a Yb 3+ Doped CsPbBr 3 The preparation method of the PMSCs comprises the following steps:
weighing CsBr and PbBr according to a proportion 2 Then dissolving the mixture in a solvent to obtain a mixed solution 1;
oleic acid and oleylamine are sequentially added into the mixed solution 1 according to a proportion, and a mixed solution 2 is obtained after dissolution;
weighing Yb-containing materials according to a proportion 3+ Adding the compound into the mixed solution 2, and dissolving to obtain a precursor solution;
injecting the precursor solution into an antisolvent to obtain Yb 3+ Doped CsPbBr 3 PMSCs solution;
high-speed centrifugal washing purification of the Yb 3+ Doped CsPbBr 3 PMSCs solution to Yb 3+ Doped CsPbBr 3 PMSCs。
Preferably, csBr and PbBr 2 The mass ratio of the substances is (0.5-1.2): 1, wherein the solvent is dimethyl sulfoxide or N, N-dimethylformamide, pbBr 2 And the ratio of the addition amount of the solvent was 0.02mmol: (0.1-1.1) mL.
PreferablyOleic acid and PbBr 2 The ratio of the amounts of the substances is (0.2 to 0.8): 1, oleylamine and PbBr 2 The ratio of the amounts of the substances is (0.1 to 0.6): 1.
preferably, the lanthanide rare earth Yb 3+ Compound(s) and PbBr 2 The ratio of the amounts of the substances is (0.04-0.1): 1.
Preferably, the antisolvent is any one of n-hexane, toluene, dichloromethane and chloroform, and the volume ratio of the precursor solution to the antisolvent is (0.1-0.5): (2-10).
Preferably, the rotating speed of high-speed centrifugation is 6000-12000 r/min, and the separated and purified Yb is obtained by high-speed centrifugation for 15-20min each time and supernatant fluid after high-speed centrifugation each time 3+ Doped CsPbBr 3 PMSCs are stored in a refrigerator at 0-5 ℃.
Preferably, the dissolving treatments are all stirring and dissolving at normal temperature; yb-containing 3+ The compound of (a) is Yb (NO) 3 ) 3 ·5H 2 O、 Yb 2 (SO 4 ) 3 、YbBr 3 、YbCl 3 And YbI 3 One or a mixture of both.
The invention also provides the Yb prepared by the preparation method 3+ Doped CsPbBr 3 PMSCs。
The invention also provides Yb prepared by the preparation method 3+ Doped CsPbBr 3 PMSCs or Yb as described above 3+ Doped CsPbBr 3 The application of PMSCs in the near infrared luminescence field.
The invention also provides a photoelectric device, which comprises Yb prepared by the preparation method 3+ Doped CsPbBr 3 PMSCs, or Yb as described above 3+ Doped CsPbBr 3 PMSCs。
The invention adopts the technical proposal has the advantages that:
yb of the present invention 3+ Doped CsPbBr 3 The preparation method of PMSCs adopts ligand-assisted reprecipitation (LAPR) technology at normal temperature, and uses CsBr and PbBr 2 As raw materials, oleic acid and oleylamine are used as surface passivation ligandsYb containing lanthanide rare earth 3+ The compound of (2) is a doped compound. Wherein, the addition of oleic acid is-COO - Can effectively passivate Cs + And Pb 2+ Addition of oleylamine-NH 3 + Can effectively passivate Br - Doping Yb containing lanthanide rare earth ions 3+ Can effectively replace CsPbBr 3 Pb in PMSCs Structure 2+ . Furthermore, the oleic acid and oleylamine ligands not only can passivate surface defects to stabilize CsPbBr 3 The effect of PMSCs can also control CsPbBr 3 The growth rate of PMSCs inhibits cluster nucleation; by reacting ligands and Yb-containing 3+ Fine regulation of the compound addition amount and the anti-solvent dripping time, thereby controlling the reaction to generate Yb with good stability and optical performance 3+ Doped CsPbBr 3 PMSCs; the preparation method has the characteristics of simple process and easy operation, and can be used for processing solution.
Yb of the present invention 3+ Doped CsPbBr 3 The PMSCs and lanthanide rare earth ions are doped into the PMSCs structure due to the abundant 4f energy level and electron configuration, so that the stability and photoelectric performance of the PMSCs can be remarkably improved, and the characteristics are mainly due to the fact that electrons in the 4f shell layer are effectively shielded by electrons in the external 5s and 5p shell layers. In addition, the rare earth ion luminescence has narrower half-peak width of the emission peak, longer luminescence decay life which can reach several microseconds, and can effectively widen the luminescence range of PMSCs, thereby improving the optical performance of PMSCs. Pb present in PMSCs 2+ Is toxic heavy metal ion, is irreversible to environmental pollution, and mainly adopts Yb 3+ Has strong light absorption advantage to near infrared light and is based on Yb 3+ Ratio Pb 2+ The ion radius is small, and Pb can be effectively doped and replaced 2+ The shrinkage of the PMSCs structure is caused to lead the binding energy between anions and cations in the structure to be enlarged, thereby effectively regulating and controlling the intrinsic luminescence enhancement of the PMSCs, improving the stability of the PMSCs structure, reducing the toxicity of lead-containing elements and widening the spectrum application range.
The invention uses Yb 3+ Doping of lanthanide rare earth ions, and CsPbBr can be effectively realized based on f-f transition of rare earth ions 3 PMSCs emit light efficiently in the near infrared band,can be applied to the near infrared luminescence field, and also provides a new method and a new idea for the design and development of high-efficiency multifunctional perovskite cluster-based photoelectric devices.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows Yb in example 1 of the present invention 3+ Doped CsPbBr 3 The ultraviolet absorption spectrum and the fluorescence emission spectrum of PMSCs are tested to obtain a result graph, wherein (a) is Yb 3+ Doped CsPbBr 3 Ultraviolet absorption spectrum and fluorescence emission spectrum of PMSCs in ultraviolet-visible light range, (b) graph Yb 3+ Doped CsPbBr 3 Fluorescence emission spectra of PMSCs in the near infrared range;
FIG. 2 shows Yb in comparative example 1 of the present invention 3+ Doped CsPbBr 3 Ultraviolet absorption spectrum and fluorescence emission spectrum test result graphs of Perovskite Quantum Dots (PQDs) in the wavelength range of 350-650 nm;
FIG. 3 shows undoped CsPbBr of comparative example 2 of the present invention 3 The test result graph of the ultraviolet absorption spectrum and the fluorescence emission spectrum of PMSCs in the wavelength range of 350-650 nm;
FIG. 4 is a graph showing the time-dependent fluorescence quantum yield of the stability of the products prepared in examples 1 to 4 and comparative examples 1 to 3 according to the present invention, wherein (a) the graph corresponds to Yb prepared in examples 1 to 4 3+ Doped CsPbBr 3 PMSCs, (b) plot corresponds to the products prepared in examples 1-3.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a Yb 3+ Doped CsPbBr 3 The preparation method of the PMSCs comprises the following steps:
weighing CsBr and PbBr according to a proportion 2 Then dissolving the mixture in a solvent to obtain a mixed solution 1;
oleic acid and oleylamine are sequentially added into the mixed solution 1 according to a proportion, and a mixed solution 2 is obtained after dissolution;
weighing Yb-containing materials according to a proportion 3+ Adding the compound into the mixed solution 2, and dissolving to obtain a precursor solution;
injecting the precursor solution into an antisolvent to obtain Yb 3+ Doped CsPbBr 3 PMSCs solution;
high-speed centrifugal washing purification of the Yb 3+ Doped CsPbBr 3 PMSCs solution to Yb 3+ Doped CsPbBr 3 PMSCs。
Wherein CsBr and PbBr 2 The mass ratio of the substances is (0.5-1.2): 1, preferably 0.8 to 1.1. The solvent is dimethyl sulfoxide (DMSO) or N, N-Dimethylformamide (DMF), pbBr 2 And the ratio of the addition amount of the solvent was 0.02mmol: (0.1-1.1) mL, when PbBr 2 When the amount of the substance (B) is 0.02mmol, the solvent addition volume is preferably 0.1mL, 0.3mL, 0.5mL, 0.7mL, 0.9mL or 1.1mL, more preferably 0.3mL, 0.5mL and 0.7mL. CsBr and PbBr 2 The dissolution of (2) is stirring dissolution at normal temperature, and the stirring time is about 20min.
Oleic acid and PbBr 2 The ratio of the amounts of the substances is (0.2 to 0.8): 1, preferably (0.4 to 0.7): 1, a step of; oleylamine and PbBr 2 The ratio of the amounts of the substances is (0.1 to 0.6): 1, preferably (0.2 to 0.4): 1. the dissolution of oleic acid and oleylamine is stirring dissolution at normal temperature, and the stirring time is about 30min.
Yb containing lanthanide rare earth 3+ Compound(s) and PbBr 2 The ratio of the amounts of the substances is (0.04-0.1): 1, preferably (0.05 to 0.08): 1. yb-containing 3+ The compound of (2) may be selected as Yb (NO) 3 ) 3 ·5H 2 O、Yb 2 (SO 4 ) 3 、 YbBr 3 、YbCl 3 And YbI 3 One or a mixture of both. Yb-containing 3+ The dissolution of the compound is rapid stirring dissolution at normal temperature, and the stirring time is about 10min.
The antisolvent is any one of n-hexane, toluene, dichloromethane and chloroform, and is preferably toluene or dichloromethane. The volume ratio of the precursor solution to the antisolvent is (0.1-0.5): (2 to 10), preferably (0.2 to 0.5): (4-8). The method for injecting the precursor solution into the antisolvent comprises the following steps: and placing a glass bottle of the anti-solvent with a stirrer on a stirring table for stirring, measuring the precursor solution by a liquid transfer device, rapidly injecting the precursor solution into the anti-solvent at one time, and rapidly stirring for 5-10min at normal temperature.
The rotation speed of high-speed centrifugation is 6000-12000 r/min, preferably 8000-10000 r/min, and the Yb after separation and purification is obtained by high-speed centrifugation for 15-20min each time and supernatant fluid after high-speed centrifugation each time 3+ Doped CsPbBr 3 PMSCs are stored in a refrigerator at 0-5 ℃.
The invention also provides the Yb prepared by the preparation method 3+ Doped CsPbBr 3 PMSCs。
The invention also provides Yb prepared by the preparation method 3+ Doped CsPbBr 3 PMSCs or Yb as described above 3+ Doped CsPbBr 3 The application of PMSCs in the near infrared luminescence field.
The invention also provides a photoelectric device, which comprises Yb prepared by the preparation method 3+ Doped CsPbBr 3 PMSCs, or Yb as described above 3+ Doped CsPbBr 3 PMSCs。
Example 1
Yb (Yb) 3+ Doped CsPbBr 3 PMSCs, prepared as follows:
the mass ratio of the substances in the glove box is respectively 1:1 cesium bromide (CsBr) and lead bromide (PbBr) 2 ) Then transferring the mixture into a solvent containing dimethyl sulfoxide (DMSO) and rapidly stirringTo complete dissolution, wherein PbBr 2 The amount of the substance was 0.02mmol, and the volume of dimethyl sulfoxide (DMSO) solvent was 0.5mL, to obtain a mixed solution 1;
then, the organic carboxylic acid Oleic Acid (OA) and the organic amine oleylamine (OAm) were added to the mixed solution 1 in order and rapidly stirred until dissolved, wherein the addition amount of Oleic Acid (OA) and PbBr 2 The mass ratio of the substances is 0.5:1, the addition amount of the organic amine oleylamine (OAm) and PbBr 2 The mass ratio of the substances is 0.3:1, obtaining a mixed solution 2;
subsequently, a certain amount of Yb-containing 3+ Rare earth compound YbBr 3 Adding into the mixed solution 2 and stirring rapidly until dissolved, wherein YbBr 3 And PbBr 2 The mass ratio of the substances is 15:1, obtaining a precursor solution;
according to the volume ratio of the precursor solution to the antisolvent dichloromethane of 1:5, rapidly injecting the precursor solution into the rapidly stirred dichloromethane antisolvent, wherein the volume of the antisolvent dichloromethane is 5mL; covering and stirring at room temperature for reacting for 5-10min to obtain Yb 3+ Doped CsPbBr 3 PMSCs solution;
the Yb obtained by the reaction is reacted 3+ Doped CsPbBr 3 Performing centrifugal washing and purifying treatment on PMSCs solution at 10000r/min, centrifuging for 10min each time to obtain supernatant, and centrifuging for 3 times to obtain purified Yb 3+ Doped CsPbBr 3 PMSCs are finally stored in a refrigerator at 0-5 ℃.
Example 2
Yb (Yb) 3+ Doped CsPbBr 3 PMSCs, the preparation of which differs from that of example 1 only in that: the solvent is N, N-Dimethylformamide (DMF), the antisolvent is toluene, and other processes are controlled identically.
Example 3
Yb (Yb) 3+ Doped CsPbBr 3 PMSCs, the preparation of which differs from that of example 1 only in that: addition amount of organic amine (OAm) and PbBr 2 The mass ratio of the substances is 0.4:1, the other process controls are the same.
Example 4
Yb (Yb) 3+ Doped CsPbBr 3 PMSCs, the preparation of which differs from that of example 1 only in that: ybBr 3 And PbBr 2 The mass ratio of the substances is 10:1, the other process controls are the same.
Comparative example 1
Yb (Yb) 3+ Doped CsPbBr 3 PQDs, the process of preparation differs from that of example 1 only in: no organic carboxylic acid Oleic Acid (OA) was added and the other process controls were identical.
Comparative example 2
Undoped CsPbBr 3 PMSCs, the preparation of which differs from that of example 1 only in that: yb-containing 3+ The compound of (a) is Yb (NO) 3 ) 3 ·5H 2 O, other process controls are identical.
Comparative example 3
Yb (Yb) 3+ Doped CsPbBr 3 PQDs, the process of preparation differs from that of example 1 only in: no organoamine oleylamine (OAm) was added and the other process controls were identical.
The performance test and results are as follows:
(1) The products prepared in example 1, comparative example 1 and comparative example 2 were subjected to ultraviolet absorption spectrum and fluorescence emission spectrum tests using an ultraviolet-visible-near infrared spectrophotometer and a fluorescence spectrophotometer instrument.
FIG. 1 shows Yb in example 1 3+ Doped CsPbBr 3 The ultraviolet absorption spectrum and the fluorescence emission spectrum of PMSCs are tested to obtain a result graph, wherein (a) is Yb 3+ Doped CsPbBr 3 Ultraviolet absorption spectrum and fluorescence emission spectrum of PMSCs in ultraviolet-visible light range, (b) graph Yb 3+ Doped CsPbBr 3 The fluorescence emission spectrum of PMSCs in the near infrared range. As can be seen from the graph, yb in example 1 3+ Doped CsPbBr 3 The characteristic peaks of the ultraviolet absorption spectrum and the fluorescence emission spectrum of PMSCs are 418nm and 420/978 nm, respectively.
FIG. 2 shows Yb in comparative example 1 3+ Doped CsPbBr 3 The ultraviolet absorption spectrum and fluorescence emission spectrum of the PQDs in the wavelength range of 350-650nm are shown,as can be seen from the figure, the characteristic peaks of the ultraviolet absorption spectrum and the fluorescence emission spectrum are 508nm and 519nm, respectively.
FIG. 3 is undoped CsPbBr of comparative example 2 3 The characteristic peaks of the ultraviolet absorption spectrum and the fluorescence emission spectrum of the PMSCs in the wavelength range of 350-650nm are 510nm and 515nm respectively.
(2) The stability of the products prepared in examples 1-4 and comparative examples 1-3 was tested for fluorescence quantum yield using a fluorescence spectrophotometer under the following experimental conditions: the relative air humidity at room temperature was 80%. Table 1 counts the initial values of fluorescence quantum yields and the values after one month (30 days) for the stability of the products prepared in examples 1-4 and comparative examples 1-3.
TABLE 1 fluorescent Quantum yield test results for stability of the products prepared in examples 1-4 and comparative examples 1-3
| Initial value of fluorescence quantum yield% | Fluorescence quantum yield after one month% | |
| Example 1 | 90％ | 88％ |
| Example 2 | 89％ | 87％ |
| Example 3 | 87％ | 85％ |
| Example 4 | 85％ | 80％ |
| Comparative example 1 | 8％ | 1％ |
| Comparative example 2 | 76％ | 28％ |
| Comparative example 3 | 12％ | 3％ |
The time-dependent fluorescence quantum yield curves of the stability of the products prepared in examples 1 to 4 and comparative examples 1 to 3 are shown in FIG. 4, in which (a) is a graph of Yb prepared in examples 1 to 4 3+ Doped CsPbBr 3 The initial values of fluorescence quantum yield for one month (30 days) for PMSCs were reduced from initial 90%, 89%, 87% and 85% to 88%, 87%, 85% and 80%, respectively, exhibiting good stability. (b) The graphs show CsPbBr prepared in comparative examples 1 to 3 3 The initial values of fluorescence quantum yields for one month (30 days) in the PQDs test were reduced from initial 8%, 76% and 12% to 1%, 28% and 3%, respectively, with poor stability and easy decomposition. Comparative example 1 and comparative example 3 were difficult to control for CsPbBr synthesis because no ligand Oleic Acid (OA) and oleylamine (OAm) were added, respectively, and no ligand synergistic passivation surface defects were present only for single ligand passivation surface defects 3 PMSCs to produce CsPbBr with poor stability 3 PQDs. Comparative example 2 since Yb was contained 3+ Compound YbBr 3 Replacement of Yb (NO) 3 ) 3 ·5H 2 O, reactionUndoped CsPbBr is generated 3 PMSCs, while the surface ligand passivates surface defects and plays a certain role in stabilizing surface coating, yb cannot be synthesized 3+ Doped CsPbBr 3 PMSCs。
(3) The products prepared in example 1 and comparative example 2 were tested for stability in the polar solvent isopropanol, with a sample solution volume to isopropanol volume ratio of 1:1.
As a result of the stability analysis, the initial values of the fluorescence quantum yields of the samples of example 1 and comparative example 2 were reduced from 90% and 76% to 82% and 21%, respectively. Yb in example 1 3+ Doped CsPbBr 3 PMSCs samples have better stability and optical properties than undoped CsPbBr 3 PMSCs sample showing lanthanide rare earth Yb 3+ Doping can effectively improve CsPbBr 3 Stability and optical properties of PMSCs.
The invention adopts the technical proposal has the advantages that:
yb of the present invention 3+ Doped CsPbBr 3 The preparation method of PMSCs adopts ligand-assisted reprecipitation (LAPR) technology at normal temperature, and uses CsBr and PbBr 2 Oleic Acid (OA) and oleylamine (OAm) are used as surface passivation ligands and contain Yb 3 + The compound of (2) is rare earth doped compound, and the addition of oleic acid is-COO - Can effectively passivate Cs + And Pb 2+ Addition of oleylamine-NH 3 + Can effectively passivate Br - Doped with Yb-containing 3+ Can effectively replace CsPbBr 3 Pb in PMSCs Structure 2+ Oleic acid and oleylamine ligands not only can passivate surface defects to stabilize PMSCs, but also can control the growth speed of the PMSCs, and inhibit cluster nucleation to stabilize the PMSCs structure; by reacting ligands and Yb-containing 3+ Fine control of the compound addition amount and the anti-solvent dropping time, thereby generating Yb with good stability and optical performance by reaction 3+ Doped CsPbBr 3 PMSCs; the preparation method has the characteristics of simple process and easy operation, and can be used for processing solution.
Yb of the present invention 3+ Doped CsPbBr 3 PMSCsThe lanthanide rare earth ions are doped into the PMSCs structure due to rich 4f energy level and electron configuration, so that the stability and photoelectric performance of the PMSCs can be remarkably improved, and the characteristics are mainly due to the fact that electrons in the 4f shell layer are effectively shielded by electrons in the external 5s and 5p shell layers. In addition, the rare earth ion luminescence has narrower half-peak width of the emission peak, longer luminescence decay life which can reach several microseconds, and can effectively widen the luminescence range of PMSCs, thereby improving the fluorescence quantum yield of PMSCs. Pb present in PMSCs 2+ Is toxic heavy metal ion, is irreversible to environmental pollution, and mainly adopts Yb 3+ Has strong light absorption advantage to near infrared light and is based on Yb 3+ Ratio Pb 2+ The ion radius is small, and Pb can be effectively doped and replaced 2+ The shrinkage of the PMSCs structure is caused to lead the binding energy between anions and cations in the structure to be enlarged, thereby effectively regulating and controlling the intrinsic luminescence enhancement of the PMSCs, improving the stability of the PMSCs structure, reducing the toxicity of lead-containing elements and widening the spectrum application range.
The invention uses Yb 3+ The doping of lanthanide rare earth ions can effectively realize the efficient luminescence of PMSCs in the near infrared band based on the f-f transition of rare earth ions, can be applied to the near infrared luminescence field, and provides a new method and a new idea for the design and development of efficient multifunctional perovskite cluster-based photoelectric devices.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (6)
1. Yb (Yb) 3+ Doped CsPbBr 3 The preparation method of the PMSCs is characterized by comprising the following steps:
weighing CsBr and PbBr according to a proportion 2 Then it is put intoDissolving in a solvent to obtain a mixed solution 1;
oleic acid and oleylamine are sequentially added into the mixed solution 1 according to a proportion, and a mixed solution 2 is obtained after dissolution;
weighing Yb-containing materials according to a proportion 3+ Adding the compound into the mixed solution 2, and dissolving to obtain a precursor solution;
injecting the precursor solution into an antisolvent to obtain Yb 3+ Doped CsPbBr 3 PMSCs solution;
high-speed centrifugal washing purification of the Yb 3+ Doped CsPbBr 3 PMSCs solution to Yb 3+ Doped CsPbBr 3 PMSCs；
CsBr and PbBr 2 The mass ratio of the substances is (0.5-1.2): 1, wherein the solvent is dimethyl sulfoxide or N, N-dimethylformamide, pbBr 2 And the ratio of the addition amount of the solvent was 0.02mmol: (0.1-1.1) mL;
oleic acid and PbBr 2 The ratio of the amounts of the substances is (0.2 to 0.8): 1, oleylamine and PbBr 2 The ratio of the amounts of the substances is (0.1 to 0.6): 1, a step of;
yb-containing 3+ Compound(s) and PbBr 2 The ratio of the amounts of the substances is (0.04-0.1): 1, a step of;
the antisolvent is any one of normal hexane, toluene, methylene dichloride and chloroform, and the volume ratio of the precursor solution to the antisolvent is (0.1-0.5): (2-10);
the rotating speed of high-speed centrifugation is 6000-12000 r/min;
yb-containing 3+ The compound of (C) is YbBr 3 。
2. The Yb of claim 1 3+ Doped CsPbBr 3 The preparation method of PMSCs is characterized in that the Yb after separation and purification is obtained by high-speed centrifugation for 15-20min each time and supernatant after high-speed centrifugation each time 3+ Doped CsPbBr 3 PMSCs are stored in a refrigerator at 0-5 ℃.
3. The Yb of claim 1 3+ Doped CsPbBr 3 PMSCsThe preparation method is characterized in that the dissolution treatment is stirring dissolution at normal temperature.
4. Yb obtained by the process of any one of claims 1-3 3+ Doped CsPbBr 3 PMSCs。
5. Yb prepared by the method of any one of claims 1-3 3+ Doped CsPbBr 3 PMSCs or Yb of claim 4 3+ Doped CsPbBr 3 The application of PMSCs in the near infrared luminescence field.
6. An optoelectronic device, characterized by: the photoelectric device comprises Yb prepared by the preparation method of any one of claims 1-3 3+ Doped CsPbBr 3 PMSCs, or Yb as claimed in claim 4 3+ Doped CsPbBr 3 PMSCs。
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