CN110540209A

CN110540209A - Nano composite material FAPBBr3/SiO2, and preparation method and application thereof

Info

Publication number: CN110540209A
Application number: CN201910782478.7A
Authority: CN
Inventors: 唐孝生; 卞瑶; 杜鹃; 张孟; 叶怀宇; 张国旗
Original assignee: Shenzhen Third Generation Semiconductor Research Institute
Current assignee: Southwest University of Science and Technology
Priority date: 2019-08-23
Filing date: 2019-08-23
Publication date: 2019-12-06
Anticipated expiration: 2039-08-23
Also published as: CN110540209B

Abstract

The invention belongs to the technical field of laser, and relates to a nano composite material FAPBBr3/SiO2, a preparation method and application thereof in a two-photon pumping nano random laser, wherein the preparation method comprises the following steps: mixing absolute ethyl alcohol, deionized water, ammonia water and tetraethyl orthosilicate (TEOS), stirring, purifying and drying to obtain SiO2 nanospheres; injecting the mixture into anhydrous ethanol and 3-aminopropyl triethoxysilane (APTES), purifying and drying to obtain aminated SiO2 nanospheres; dissolving FABr and PbBr2 in DMF, stirring thoroughly, pouring aminated SiO2 nanospheres into the prepared solution to prepare quantum dot solution A; adding oleic acid and oleylamine into the quantum dot solution A, and stirring to prepare a solution B; dripping a small amount of the solution B into a trichloromethane solution; and centrifugally purifying the precipitated product solution to obtain the nano composite material FAPBBr3/SiO 2.

Description

Nano composite material FAPBBr3/SiO2, and preparation method and application thereof

Technical Field

the invention relates to the technical field of laser, in particular to application of a composite nano material FAPBBr3/SiO2 in the field of a nano random laser.

Background

in recent years, nano lasers have attracted more and more attention in the field of nano materials, and are widely applied to the fields of super-resolution biomedical imaging, ultra-high density data storage, integrated optical chips and the like. The two-photon pumping laser does not need phase matching, and plays an important role in the fields of three-dimensional material manufacturing and biology.

nanocrystal Quantum Dots (QDs) derive low dimensional properties with significant advantages due to size effects, quantum confinement effects, macroscopic quantum tunneling and surface effects, such as narrow emission peaks and simple synthesis methods, with tremendous potential in low-threshold laser applications.

Halide perovskite quantum dots which have been developed in recent years are particularly excellent as optical gain materials, the common combination advantage of colloidal quantum dots and halides is shown, and the photoluminescence performance of the system has the advantages of high external quantum efficiency, no scintillation in luminescence, low pumping threshold of stimulated radiation light and the like. For perovskite quantum dots with higher luminous efficiency, research mainly focuses on FAPBX3 quantum dots with cubic crystal orientation, for example, FAPBR 3 nano-particles with cubic crystal orientation are synthesized by an ultrasonic oscillation method in Jeunghee Park, and FAPBR 3 quantum dots with cubic crystal orientation are synthesized by a Maksym V.Kovalenko group by a thermal injection method, the size is adjustable within 5-12 nm, the full width at half maximum is less than 22nm, and the highest luminous efficiency can reach 85%.

However, the instability of FAPbX3 quantum dots has hindered the further development of optoelectronic devices based on FAPbX3 perovskite quantum dots. In the prior art, the purpose of improving stability is achieved by isolating water and oxygen through a method of wrapping quantum dots with an inert encapsulant, but the thickness of a shell layer is difficult to control through wrapping. On the other hand, SiO2 can be used as a good laser medium due to its good chemical stability and strong scattering property to light, and can realize low-threshold and ultra-stable emission of wavelength-tunable upconversion laser (Advanced Optical Materials,2018,6(3): 1700997), however, the preparation of laser usually has high requirements for the resonant cavity and the process conditions of the preparation.

Disclosure of Invention

In view of the above, the present invention aims to provide a method for preparing a nanocomposite FAPbBr3/SiO2, a method for preparing the same, and an application of the nanocomposite FAPbBr3/SiO2 as a pump nano random laser.

the preparation method of the nano composite material FAPBBr3/SiO2 comprises the following steps:

(1) Mixing absolute ethyl alcohol, deionized water, ammonia water and tetraethyl orthosilicate (TEOS), stirring and purifying, then carrying out purification and centrifugation operation by using the ethanol, and drying to obtain SiO2 nanospheres;

(2) Injecting the SiO2 nanospheres prepared in the step (1) into absolute ethyl alcohol and 3-aminopropyl triethoxysilane (APTES), stirring, purifying and drying to obtain aminated SiO2 nanospheres;

(3) dissolving FABr and PbBr2 in DMF, and stirring thoroughly; pouring the aminated SiO2 nanospheres prepared in the step (2) into the prepared solution and fully stirring to prepare a quantum dot solution A;

(4) adding oleic acid and oleylamine into the quantum dot solution A prepared in the step (3) and stirring to prepare a solution B;

(5) dripping the solution B prepared in the step (4) into a trichloromethane solution; and centrifugally purifying the precipitated product solution, and centrifugally purifying with toluene to obtain the nano composite material FAPBBr3/SiO 2.

Further, the volume ratio of ammonia to tetraethyl orthosilicate (TEOS) in the step (1) affects the size of the silicon spheres, the volume ratio of the ammonia to the tetraethyl orthosilicate (TEOS) is preferably 1: 1-3, and the volume ratio of absolute ethyl alcohol, deionized water, ammonia water and tetraethyl orthosilicate (TEOS) in the step (1) is preferably as follows: 1:0.1-0.5:0.02-0.06: 0.02-0.06;

Further, the mixing, stirring and purifying in the step (1) comprises stirring for 6-8 hours, and then carrying out purification operation for 2-5 minutes at the rotating speed of 8000 r/s; preferably, the purifying centrifugation with ethanol and drying comprises purifying with ethanol at 8000r/s for 2-5 min, and drying after three times of purifying centrifugation;

further, the weight of the nanospheres in the step (2) is 40-100 mg, the volume ratio of ethanol to 3-Aminopropyltriethoxysilane (APTES) is 1:0.06-0.2,

further, the stirring, purifying and drying in the step (2) comprises continuously stirring for 6-8 hours, and then carrying out purification operation for 2-5 minutes at a rotating speed of 8000 r/s; preferably, the purifying centrifugation with ethanol and drying comprises purifying with ethanol at 8000r/s for 2 min, and drying after three times of purifying centrifugation;

further, in the step (3), the weight-volume ratio of FABr, PbBr2, SiO2 and DMF silicon spheres is 10-15:30-45:45-55:1(mg: mg: mg: ml);

Further, the fully stirring in the step (3) comprises continuously stirring for 5 minutes;

Further, the volume ratio of the quantum dot solution A to the oleic acid and the oleylamine in the step (4) is 1:100-300: 30-50;

Further, the volume ratio of the quantum dot solution A to the oleic acid and the oleylamine in the step (4) is 1: 0.4: 0.08;

Further, the rotating speed of the stirring in the step (4) is 8000 r/s; preferably, the stirring time is 2 minutes;

further, the volume ratio of the solution B to the trichloromethane solution in the step (5) is 1: 10-50;

Further, the volume ratio of the solution B to the trichloromethane solution in the step (5) is 0.1: 3;

Further, the centrifugal purification in the step (5) includes a first centrifugal purification of the precipitated product solution at a rotational speed of 9000r/s for 2 minutes, followed by a centrifugal purification with toluene at the same rotational speed for the same period of time.

the silica nanospheres have a relatively small volume, the diameter of 200-400nm, which cannot be directly quantified from the volume ratio, and the weight of the silica nanospheres is not limited, but the silica nanospheres have a range of 50-100 mg per 2ml of solution. Beyond or below this range, the scattering effect of the nanospheres is poor.

a nano composite material FAPBBr3/SiO2 is characterized in that the preparation method comprises the following steps: the method comprises the following steps:

the silica nanospheres have a smaller volume, the diameter of 200-400nm, which cannot be directly quantified from the volume ratio, and the weight of the silica nanospheres is not limited, but the silica nanospheres have a range of 50-100 g in each 2ml of solution.

On the basis of a room temperature redeposition method, quantum dots are obtained by utilizing an amine chain-guided in-situ growth method, and a nano composite material FAPBR 3/SiO2 is obtained by introducing aminated SiO2 silicon spheres; thereby successfully exciting the two-photon random laser at room temperature while improving the light stability of the quantum dots. The preparation method is an amine chain-oriented in-situ growth method, and the prepared quantum dots are separated from each other, so that the light stability of the quantum dots is effectively enhanced; on the other hand, the refractive index of SiO2 is about 1.5, the refractive index of FAPBBr3 is about 2.5, and the large difference of the refractive indexes has strong scattering property for light. Photons of a laser light source are scattered randomly and continuously in a high-density grain boundary, and a part of the photons returns to an original light path incidence point, so that a closed loop is formed, when the optical gain is larger than the loss, laser oscillation is carried out at the resonance frequency of a corresponding feedback circuit, so that two-photon random laser is realized, the random laser threshold of the prepared material can reach 540 mu J/cm2, and the quality factor is 1720. The whole process adopts a room temperature method, is simple and controllable, is easy to operate, the prepared product has high crystallization degree and good uniformity, and the nano composite material FAPBR 3/SiO2 is applied to a two-photon pumping nano random laser under the condition of not additionally adding laser resonance, so that the perovskite-based low-cost random laser device can be realized by a simple and convenient method, and a new solution is provided for frequency rising conversion. The invention overcomes the problems that the general two-photon laser is harsh in the preparation process condition and needs an additional laser resonance cavity, and the like, and can realize the normal-temperature preparation of the laser without an additional laser gun.

drawings

FIG. 1 is a schematic flow chart of the preparation of FAPBR 3/SiO2 nano composite material in the invention.

FIG. 2 is an X-ray diffraction pattern of FAPBR 3 quantum dots and FAPBR 3/SiO2 composite material.

FIG. 3 is a scanning electron microscope picture of FAPBR 3/SiO2 nanocomposite in the invention.

FIG. 4 is a scanning electron microscope picture and an energy dispersion spectrum of the single-particle FAPBR 3/SiO2 composite material.

FIG. 5 shows (a) fluorescence spectrum and (b) absorption spectrum of FAPBR 3 and FAPBR 3/SiO2 in the present invention.

FIG. 6 is a fluorescence stability map of FAPBBr3 quantum dots and FAPBBr3/SiO2 nanocomposite material under a room temperature environment with 75% humidity.

FIG. 7 is a fluorescence lifetime map of FAPBR 3 and FAPBR 3/SiO2 in the present invention.

FIG. 8 is a two-photon laser mechanism and test (lasing) spectrum of FAPBR 3/SiO2 composite nanomaterial of the present invention.

Detailed Description

in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example 1:

1. preparation and amination of silicon spheres: 20ml of absolute ethyl alcohol, 2ml of deionized water, 0.4ml of ammonia water and 0.4ml of Tetraethylorthosilicate (TEOS) are taken. Stirring for 1 hour, then carrying out purification operation at 2000r/s for 2 minutes, then carrying out purification centrifugation operation for three times by using ethanol at the same rotating speed and time length, and drying. 0.5 g of nanosphere was injected with 10ml of absolute ethanol and 0.6ml of 3-Aminopropyltriethoxysilane (APTES), and the mixture was stirred continuously for 1 hour and purified and dried in the same manner to obtain aminated SiO2 nanosphere.

2. 10mg of FABr and 30mg of PbBr2 were dissolved in 1ml of DMF and the solution was stirred well. 45mg of aminated SiO2 silica spheres were poured into the solution and stirred well.

3. 1ml of the precursor solution was added with 100ml of oleic acid and 30ml of oleylamine, and stirred for 5 minutes. 100 microliter of FAPBBr3/SiO2 nucleating solution is added dropwise into 1ml of chloroform solution by stirring. The precipitated product solution was subjected to a first centrifugal purification at 8000r/s for 1 minute. Then, the mixture is centrifugally purified for 3 times by toluene at the same rotating speed, so that FAPBR 3/SiO2 is obtained.

Example 2:

1. preparation and amination of silicon spheres:

20ml of absolute ethanol, 10ml of deionized water, 1.2ml of ammonia water and 1.2ml of Tetraethylorthosilicate (TEOS) are taken. Stirring for 8 hours, then carrying out purification operation for 5 minutes at the rotating speed of 8000r/s, then carrying out purification centrifugation operation for three times by using ethanol at the same rotating speed and time length, and drying. 2 g of nanospheres were injected with 20ml of absolute ethanol and 4ml of 3-Aminopropyltriethoxysilane (APTES), stirred continuously for 8 hours, and purified and dried in the same manner to obtain aminated SiO2 nanospheres.

2. 60mg of FABr and 180mg of PbBr2 were dissolved in 4ml of DMF and stirred well. 220mg of aminated SiO2 silica spheres were poured into the solution and stirred well.

3. 1ml of the precursor solution was added with 300ml of oleic acid and 50ml of oleylamine, and stirred for 5 minutes. 100 microliter of FAPBBr3/SiO2 nucleating solution is added dropwise into 5ml of chloroform solution by stirring. The precipitated product solution was subjected to a first centrifugal purification at a rotational speed of 9000r/s for 5 minutes. Then, the mixture is centrifugally purified for 3 times by toluene at the same rotating speed, so that FAPBR 3/SiO2 is obtained.

example 3:

1. preparation and amination of silicon spheres:

14.8ml of absolute ethanol, 2ml of deionized water, 0.63ml of ammonia water and 1.2ml of Tetraethylorthosilicate (TEOS) were taken. Stirring for 8 hours, then carrying out purification operation for 2 minutes at the rotating speed of 8000r/s, then carrying out purification centrifugation operation for three times by using ethanol at the same rotating speed and time length, and drying. 0.6 g of nanosphere was injected with 10ml of absolute ethanol and 1ml of 3-Aminopropyltriethoxysilane (APTES), and the mixture was stirred continuously for 8 hours and purified and dried in the same manner to obtain aminated SiO2 nanosphere.

2. 22.4mg of FABr and 73.4mg of PbBr2 were dissolved in 2ml of DMF and stirred well. 100mg of aminated SiO2 silica spheres were poured into the solution and stirred well.

3. 2ml of the precursor solution was added with 400ml of oleic acid and 80ml of oleylamine, and stirred for 5 minutes. 100 microliter of FAPBBr3/SiO2 nucleating solution is added dropwise into 3ml of chloroform solution by stirring. The precipitated product solution was subjected to a first centrifugal purification at a rotational speed of 9000r/s for 2 minutes. Then, the mixture is centrifugally purified for 3 times by toluene at the same rotating speed, so that FAPBR 3/SiO2 is obtained.

The preparation process of the FAPBBr3/SiO2 nanocomposite is shown in figure 1; the structure, morphology and composition of the product obtained by the preparation method of the invention in example 3 were further characterized by X-ray powder diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), elemental line scan (EDS line scan) and elemental profile map (EDS Mapping), respectively.

XRD results show that the crystal form, the particle size distribution and the main components of the product are completely consistent with the diffraction angle corresponding to the peak position of the FAPBBr3/SiO2 composite material, so that the cubic structure of the quantum dot is not influenced by the addition of the silicon spheres (XRD is mainly related to the diffraction angle corresponding to the peak and has no relation with the intensity), as shown in figure 2.

TEM shows particle size and overall morphology, EDS line scanning detects the micro-area element composition of the hollow particles, and proves the result of XRD; FIG. 3 is (a) TEM and (b) HRTEM images and (c) HRTEM images of FAPBR 3/SiO2 nanocomposite; FIG. 4 is an HRTEM of (a) single particle FAPBBr3/SiO2 composite, (b) EDS energy spectrum, (c-e) elemental distribution image (mapping) of Pb, Br, Si.

FIG. 5 shows (a) a fluorescence spectrum and (b) an absorption spectrum of FAPBR 3 and FAPBR 3/SiO 2; FIG. 6 is a fluorescence stability map of FAPBR 3 quantum dots and FAPBR 3/SiO2 nanocomposite at room temperature; FIG. 7 shows the fluorescence lifetimes of FAPBR 3 and FAPBR 3/SiO2 and their corresponding fitted curves; compared with FAPBBr3 quantum dots, the FAPBBr3/SiO2 nano composite material has better light stability in a room temperature environment, and the fluorescence life of the nano composite material is obviously prolonged.

fig. 8 is a photograph of FAPbBr3/SiO2 composite nanomaterial (a) emitting laser, the upper left corner is a schematic diagram of a random laser luminescence mechanism, (b) an integral variation curve of FAPbBr3/SiO2 composite nanomaterial luminescence intensity enhanced with pumping energy (c) a curve of lorentz fitting to a laser spectrum; as shown in the figure, as the pumping energy is increased, the random laser threshold of the material can reach 540 uJ/cm 2, and the quality factor is 1720.

the previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. a preparation method of a nano composite material FAPBBr3/SiO2 comprises the following steps:

2. the method for preparing the nano-composite material FAPBBr3/SiO2 as claimed in claim 1, wherein the volume ratio of ammonia to tetraethyl orthosilicate (TEOS) in step (1) affects the size of the silicon spheres, and preferably the volume ratio of ethanol to deionized water to ammonia to tetraethyl orthosilicate (TEOS) in step (1) is: 1:0.1-0.5:0.02-0.06:0.02-0.06.

3. The preparation method of the nanocomposite FAPBBr3/SiO2 as claimed in claim 1, wherein the volume ratio of ethanol to 3-Aminopropyltriethoxysilane (APTES) in step (2) is 1: 0.06-0.2.

4. The preparation method of FAPBBr3/SiO2 as defined in claim 1, wherein the weight-to-volume ratio of FABr, PbBr2, SiO2 nanospheres and DMF in step (3) is 10-15:30-45:45-55:1(mg: mg: mg: ml).

5. The preparation method of the nanocomposite FAPBBr3/SiO2 as claimed in claim 1, wherein the volume ratio of the quantum dot solution A to the oleic acid and the oleylamine in the step (4) is 1:100-300: 30-50.

6. the method for preparing the nano composite material FAPBBr3/SiO2 as claimed in claim 1, wherein the volume ratio of the solution B to the trichloromethane in the step (5) is 1: 10-50.

7. The preparation method of the nano-composite material FAPBBr3/SiO2 as claimed in claim 1, wherein the mixing, stirring and purifying in step (1) comprises stirring for 6-8 hours, and then performing a purifying operation at 8000r/s for 2 minutes; the purifying and centrifuging operation with ethanol and drying include purifying operation with ethanol at 8000r/s for 2-5 min, and drying after three times of purifying and centrifuging operation.

8. a nano composite material FAPBBr3/SiO2 is characterized in that the preparation method comprises the following steps:

9. the nanocomposite FAPBBr3/SiO2 as claimed in claim 7, wherein the weight to volume ratio of FABr, PbBr2, SiO2 nanospheres and DMF in step (3) is 10-15:30-45:45-55:1(mg: mg: mg: ml).

10. A two-photon pumped nano-random laser, characterized in that its light emitting layer is made of the nanocomposite FAPbBr3/SiO2 of claim 7.