CN112484851B - Perovskite lanthanide series composite nano material, preparation method thereof and application of perovskite lanthanide series composite nano material in broadband photoelectric detector - Google Patents
Perovskite lanthanide series composite nano material, preparation method thereof and application of perovskite lanthanide series composite nano material in broadband photoelectric detector Download PDFInfo
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- G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
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Abstract
The invention discloses a perovskite lanthanide series composite nano material, a preparation method thereof and application in a broadband photoelectric detector, the metal halide perovskite and lanthanide series up-conversion composite nano material synthesized by a solution method is utilized, lanthanide series doping up-conversion nano materials (UCNPs) are an anti-Stoke process, can exactly convert low-energy near infrared light into high-energy visible light, can make up the defect that the perovskite is used for the broadband photoelectric detection, the surface of the upconversion nanometer material in the lanthanide series upconversion nanometer material doped perovskite composite nanometer material of the invention is coated with mesoporous silicon dioxide, the perovskite is formed on the surface of the mesoporous silicon by an in-situ crystallization method, has stronger quantum confinement and higher stability, can be designed into a nano sensor for detecting X-ray, ultraviolet-visible and near infrared light, the composite nano material has wide linear response to x-rays with different dose rates and UV/NIR with different power densities.
Description
Technical Field
The invention belongs to the field of photoelectric detection, and particularly relates to a perovskite lanthanide composite nanomaterial, a preparation method thereof and application of the perovskite lanthanide composite nanomaterial in a broadband photoelectric detector.
Technical Field
Organic-inorganic hybrid perovskites (CH) over the past decades3NH3PbX3X = Cl, Br, I) and all-inorganic lead-containing perovskites (CsPbX)3X = Cl, Br, I) nanocrystals have undergone a dramatic development, absorbing the attention of numerous scholars. The lead-halogen perovskite nanocrystalline material has a plurality of characteristics: such as full spectrum light regulation, narrow emission band, high photoinduced efficiency, special electronic and crystal characteristics, and endows the material with higher carrier mobility and longer carrier diffusion depth. In particular, it is possible to provide a device,full color modulation and emission make this material ideal for light emitting diodes such as LEDs, lasers, optical sensors. Photodetectors have found widespread use in biomedical sensing, camera imaging, optical communications and night vision, and can be used to record X-rays, ultraviolet-visible and near-infrared light. The most prominent sites in photodetectors are semiconductor devices that respond to different photon energies. Currently, many commercially available optical detectors mainly employ inorganic semiconductor crystals such as silicon or III-V compounds. However, these materials do not achieve ultra-wide band response to optical energy from X-ray, uv-visible coverage to near-ir. Recently, the advent of low temperature solution synthesis of metal halide perovskite materials has provided the possibility for the development of next generation photovoltaic devices. Highly sensitive photodetectors using perovskite materials as the active surface layer have been widely used for detecting ultraviolet-visible and X-rays. This is mainly due to the low manufacturing costs and the excellent optoelectronic properties such as long carrier diffusion length, high carrier mobility and large uv-vis and X-ray absorption coefficients. However, the response of perovskites in photodetectors to near-infrared light is limited because their largest absorption edges are located in the region below 850 nm of near-infrared light. Photodetectors that can respond to X-rays, near infrared light, ultraviolet-visible light simultaneously still face technical challenges.
Lanthanide series doped up-conversion nano materials (UCNPs) can convert near infrared light into ultraviolet-visible light, and are widely applied to biological imaging, multi-channel sensing, optical storage and anti-counterfeiting. Lanthanide doped up-conversion nanomaterials (UCNPs) are an anti-Stoke process that can convert just low energy near-infrared light into high energy visible light, but their inherently tight energy level separation makes them very limited in wavelength tuning. The invention designs a perovskite/lanthanide composite nanomaterial-based broadband photoelectric detector, which can realize high-efficiency multi-photon near-infrared up-conversion and X-ray scintillation. By wrapping mSiO on the surface of UCNPs2And then growing and embedding the organic-inorganic lead-based perovskite nano crystal into the mesoporous silicon by an in-situ crystallization method. The composite material not only expands a perovskite excitation light source, but also spans the limited adjustable emission of lanthanide elements to make up forThe disadvantage of the lack of a continuous emission wavelength spectrum in the lanthanide upconversion process is overcome. The invention also relates to the use of the material for the detection of X-rays, ultraviolet-visible light, near infrared light.
Disclosure of Invention
The invention aims to provide a perovskite lanthanide series composite nano material, a preparation method thereof and application of the perovskite lanthanide series composite nano material in a broadband photoelectric detector. Through reasonably combining the lanthanide and the perovskite, the functions of the lanthanide and the perovskite are fully exerted, the advantages and the disadvantages are improved, the detection of the broadband spectrum can be realized, the operation process is simple, and the sensitivity is high.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a perovskite lanthanide series composite nano material comprises the following steps:
(1) preparation of the inner core: adding a rare earth acetate mixture into oleic acid and octadecene, reacting for 30min at 150 ℃, cooling to room temperature, adding a methanol solution of NaOH and NH4F, heating to 50 ℃, continuing to react for 30min, then continuing to heat to 100 ℃, degassing the solution for 10min, and removing redundant methanol; finally, further heating to 290 ℃ under the protection of N2 for reaction for 90 min, stirring and cooling to room temperature, washing with ethanol and cyclohexane and centrifuging to obtain an inner core nano product, and dispersing in a cyclohexane solution for later use;
(2) preparing the nano particles with the core-shell structure: mixing Y (CH)3COO)3Adding into oleic acid and octadecylene, heating to 150 deg.C, reacting for 30min, and cooling to room temperature to obtain mixed solution; quickly adding the core nano product prepared in the step (1) into the mixed solution, heating to 80 ℃ for reaction for 30min, and removing cyclohexane; NaOH and NH are added4Heating the methanol solution of F to 50 ℃ for further reaction for 30min, then further heating to 100 ℃, degassing the solution for 10min, and removing the redundant methanol; finally in N2Further heating to 290 ℃ under protection, reacting for 90 min, stirring, cooling to room temperature, washing with ethanol and cyclohexane, centrifuging to obtain core-shell structured nano-particles UCNPs, and dispersing in cyclohexane solution for later use;
（3）UCNPs@mSiO2preparing a nano composite material: taking the UCNPs solution dispersed in cyclohexane in the step (2), adding CTAB and water, violently stirring in an oil bath kettle at 40 ℃ until the solution is clarified to remove cyclohexane to form UCNP-CTAB solution, adding the UCNP-CTAB solution into water, ethanol and NaOH solution, stirring and heating to 70 ℃, then adding TEOS for reaction for 10min, washing the synthesized solution with ethanol for three times, removing CTAB by an ion exchange method, and then carrying out vacuum drying to obtain UCNPs @ mSiO2A nanocomposite;
(4) MAX vacuum 60 ℃ overnight, MAX and PbX were mixed2Mixing in DMF, heating to 80 deg.C, and adding dropwise to UCNPs @ mSiO prepared in step (3)2Fully soaking the nano composite material, violently stirring for 30min, and finally drying at 95 ℃ for 30min to obtain the perovskite lanthanide series composite nano material, wherein X is one or more of Cl, Br and I.
Further, the total mole amount of the rare earth acetate mixture in the step (1) is 0.1-1 mmol, and Y (CH)3CO2)3、Yb(CH3CO2)3、Tm (CH3CO2)3According to the molar ratio of 69: 30: 1 are mixed.
Further, in the step (1), the ratio of the sodium hydroxide to the ammonium fluoride is 1: 1-2, the ratio of oleic acid to octadecene is 1: 1 to 10, NaOH and NH4The sum ratio of the volume of the methanol solution of the F to the volume of the mixture of the rare earth acetates, the oleic acid and the octadecene is 1-10: 1.
further, in the step (2), the ratio of the sodium hydroxide to the ammonium fluoride is 1: 1-2, the ratio of oleic acid to octadecene is 1: 1 to 10, NaOH and NH4Volume of methanol solution of F with Y (CH)3COO)3The volume sum ratio of oleic acid to octadecene is 1-10: 1, Y (CH)3COO)3The amount of the compound is 0.1 to 1 mmol.
The perovskite lanthanide series composite nano material is UCNPs @ mSiO2@MAPbX3Wherein X is one or more of Cl, Br and I.
The average diameter of the whole composite nano-material particle is 106nm-122 nm; wherein the core size of UCNPs is 27 + -2 nm, a lattice spacing of 3.2nm + -0.02A, a silica thickness of 30 + -2 nm, and UCNPs @ mSiO > estimated by using the BJH method2@MAPbBr3、UCNPs@mSiO2The average pore diameters of these two particles were 3.0nm and 2.5nm, respectively.
The invention uses X-ray, near infrared light and ultraviolet light to excite the perovskite lanthanide series composite nano material by changing the type and content of halogen elements to obtain a 300-800 nm broadband spectrum; the perovskite lanthanide series composite nano material is used as a broadband detector for detecting ultraviolet light, near infrared light and X rays to obtain a response curve.
The mechanism of action for realizing the broadband spectrum detection of the invention is as follows: under the excitation of near infrared light, the lanthanide doped nanocrystals emit ultraviolet-visible light through the ETU process, and the energy is transferred from the lanthanide nanocrystals to the perovskite through the ET process. Under X-ray or UV excitation, light emitted from the perovskite nanocrystals comes from electron-hole recombination between the Conduction Band (CB) and the Valence Band (VB).
The invention has the following remarkable advantages:
(1) the invention expands the excitation light source of the perovskite, fully exerts the advantages and disadvantages of lanthanide and the perovskite, and the prepared lanthanide up-conversion nano material doped mesoporous silicoperovskite nano point can realize broadband spectrum detection;
(2) the lanthanide up-conversion nanomaterial doped mesoporous silicoperovskite nanodots have good stability and strong anti-interference capability in a complex environment;
（3）mSiO2the function of passivating the shell layer is achieved, energy is protected to be effectively transferred between lanthanide series conversion nano materials, and energy quenching is prevented; and the perovskite can grow in situ in the mesopores under the action of load.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of a perovskite lanthanide composite nanomaterial;
FIG. 2 is an X-ray powder diffraction pattern (XRD) of a perovskite lanthanide composite nanomaterial;
FIG. 3 is a mapping diagram of perovskite lanthanide composite nanomaterial elements;
FIG. 4 is a graph at 278. mu. Gy s−1Under the excitation of 50 KV X-ray, the radiation luminescence curve of the perovskite lanthanide series composite nano material;
FIG. 5 is a radiative luminescence diagram of perovskite lanthanide series composite nano-materials under the excitation of near infrared light and ultraviolet light;
FIG. 6 is a linear response curve of perovskite lanthanide series composite nano-materials to near infrared light, ultraviolet light and X-rays.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Perovskite lanthanide series composite nano material UCNPs @ mSiO2@MAPbBr3The preparation of (1):
the method comprises the following steps: first 0.276 mmol Y (CH)3CO2)3、0.12 mmol Yb(CH3CO2)3、0.004 mmol Tm (CH3CO2)3Was mixed and added to a 50 mL flask containing 3 mL OA and 7 mL ODE. The mixture was heated to 150 ℃ for 30 min. After cooling to room temperature, the solution was cooled to room temperature and mixed with 2 mL of 0.5M NaOH and 4mL of 0.4M NH4Adding the methanol solution of F into the reaction solution, heating to 50 ℃, and continuing to react for 30 min. Heating the mixed solution to 100 deg.C, degassing the solution for 10min, and removing excessive methanol. Recharging N2Further heating to 290 ℃ under protection, and reacting for 90 min. After stirring and cooling to room temperature, the final core nanoproduct was dispersed in 4ml cyclohexane after washing and centrifugation with ethanol and cyclohexane several times.
Step two: 0.4 mmol of Y (CH)3CO2)33 ml of OA and 7 ml of ODE were mixed and put into a 50 ml flask and stirred uniformly, and heated to 150 ℃ to react for 30 min. After cooling to room temperature, the NaYF was synthesized dispersed in 4ml cyclohexane4Yb/Tm (30/1 mol%) was added rapidly to the reaction flask, warmed to 80 ℃ and held at this temperature for 30 min. Then, 2 mL of 0.5M NaOH and4 mL 0.4 M NH4a methanol solution of F was added to the reaction solution, followed by the same procedure as before. Finally, NaYF4:Yb/Tm (30/1mol%)@NaYF4(UCNPs) core-shell nanoparticles were washed with cyclohexane and ethanol several times by centrifugation and dispersed in 4ml cyclohexane.
Step three: first 1 ml (about 10 mg/ml) of solution of UCNPs dispersed in cyclohexane was taken and added with 0.15g CTAB and 20 ml water and stirred vigorously in a 40 ℃ oil bath until the solution cleared to remove cyclohexane and finally a solution of UCNP-CTAB was formed. 10 ml of the above sample solution was taken, mixed and added to 20 ml of water, 3 ml of ethanol and 160. mu.L of 2 mol L-1In the NaOH solution, the solution is stirred and heated to 70 ℃. 200 μ l TEOS was added, the reaction was carried out for 10min, and the resultant solution was washed three times with ethanol. Next, CTAB was removed by an ion exchange method: the synthetic UCNPs @ mSiO2Transferred to a solution containing 0.3g NH4NO3In 50 ml of ethanol, heated to 60 ℃ and reacted for 2 h. Finally, the synthesis of UCNPs @ mSiO using ethanol2The nanocomposite was washed three times and vacuum dried at 80 ℃ overnight.
Step four: MAX (X = Cl, Br or I) was vacuum 60 ℃ overnight, MAX was mixed with PbX2In DMF in the desired molar ratio and then heated to 80 ℃. Secondly, the mixed solution is gradually added dropwise to UCNPs @ mSiO2Soaking the powder thoroughly, and stirring vigorously for 30 min. And drying at 95 deg.C for 30min to obtain solid powder.
FIG. 1 is a Transmission Electron Microscope (TEM) of perovskite lanthanide composite nanomaterial, a) NaYF4:Yb/Tm(30/1 mol%)@NaYF4Electron microscopy of nanoparticles. Inset is a corresponding high resolution TEM electron micrograph showing the lattice fringes; b) coating the surface of the up-conversion nano material with mesoporous silicon; c) UCNPs @ mSiO2@MAPbBr3Typical electron microscopy of nanoparticles. d) UCNPs @ mSiO2@MAPbBr3Nanoparticles, electron microscopy highly magnified in the d-region, MAPbBr3About 0.298 nm. From fig. 1, it can be seen that the apparent mesoporous silicon structure has uniform distribution and uniform size of nanoparticles, and the average diameter of the whole composite nanoparticles is directly about 114 nm: wherein the core size of UCNPs is 27 +/-2 nm, and the crystal latticeThe spacing is about 3.2nm 0.02A and the silica thickness is about 30 + -2 nm.
As shown in FIG. 2, the perovskite lanthanide series composite nano material has good crystallinity, and all diffraction patterns of UCNPs are similar to those of standard beta-NaYF4(No. 176, PDF number 16-0344) consistent, no impurity; UCNPs @ mSiO2XRD pattern of the nanomaterial shows a peak at 22 in addition to UCNPs。There is also a larger amorphous silica structure, indicating that the silica shell has been successfully synthesized.
Fig. 3 is a mapping diagram of perovskite lanthanide series composite nanomaterial elements, which clearly shows that Si, Pb, Y, Yb and Br elements are uniformly distributed on a spherical surface, and further illustrates that perovskite has been successfully grown on the surface of mesoporous silicon.
Example 2
The nanoparticles excited by light sources with different wavelengths realize broadband spectrum
The method comprises the following steps: MAX (X = Cl, Br or I) was vacuum 60 ℃ overnight, MAX was mixed with PbX2In DMF in the desired molar ratio and then heated to 80 ℃. Secondly, the mixed solution is gradually added dropwise to UCNPs @ mSiO2Soaking the powder thoroughly, and stirring vigorously for 30 min. And drying at 95 deg.C for 30min to obtain solid powder.
Step two: according to the influence of different halogen elements and content difference on the light-emitting performance, controlling MAX and PbX according to the step one2According to the molar ratio, 8 perovskite composite materials are prepared and dissolved in cyclohexane according to a certain ratio. Wherein 1, 3 and 8 respectively represent pure chlorine, pure bromine and pure iodine. 2 represents a mixture of chlorine and bromine; 4. 5, 6, 7 represent bromine-iodine mixtures, wherein the lower the bromine content, the higher the iodine content. The 1-8 composite perovskite samples are respectively (1) MAPBClBr2；(2)MAPbCl0.5Br2.5； (3)MAPbBr3；(4)MAPbBr2.9I0.1；(5)MAPbBr2.75I0.25；(6)MAPbBr2I；(7)MAPbBr1.5I1.5；（8）MAPbI3。
Step three: the 8 solutions are respectively excited by X rays, near infrared light and ultraviolet light to obtain the luminescence spectrum or the luminescence picture thereof.
FIG. 4 shows: at 278. mu. Gy s−150 kV, indicating the radiation luminescence curve of the perovskite lanthanide series composite nano material under the X-ray excitation, and the curve shows UCNPs @ mSiO2@MAPbX3A series of tunable luminescence occurs.
FIG. 5 shows the UCNPs @ mSiO prepared by us under near infrared light or ultraviolet light excitation2@MAPbX3(X = Cl, Br or I) nanoparticles already allow color tuning. UCNPs @ mSiO2@MAPbX3The halogens in the nano-dot band gap are accurately mixed according to a certain proportion, so that the whole visible spectrum region can be covered by the nano-dot band gap.
Example 3
Establishment of linear response curves for different excitation lights
The perovskite lanthanide series composite nano material is prepared by selecting UCNPs @ mSiO2@MAPbBr3The composite material is excited with X-rays, ultraviolet light, and near infrared light as an object of study. Meanwhile, the response curve is tested by changing the X-ray radiation dose, the near infrared light excitation power and the ultraviolet light photon power at 504 nm.
Fig. 6 is a linear response curve of different excitation lights. This positive response to 980 nm light is due to NaYF4:Yb/Tm (30/1 mol%)@NaYF4Is green luminescence, is a three-photon process, and can transfer energy to MAPbBr through lanthanide up-conversion process under excitation of 980 nm3. At the same time, UCNPs @ mSiO2@MAPbBr3The composite nano material also has wide linear response to the ultraviolet light excitation with different photon powers, which shows that the composite nano material has the capability of detecting ultraviolet light. The ability of the nano material to sense X photons is further tested by adopting different doses of X rays, and the experimental result shows that UCNPs @ mSiO2@MAPbBr3The nanomaterials are also linearly related to the X-ray dose.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A preparation method of a perovskite lanthanide series composite nano material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of the inner core: adding the mixture of rare earth acetate into oleic acid and octadecene, reacting for 30min at 150 ℃, cooling to room temperature, and then adding NaOH and NH4Heating the methanol solution of F to 50 ℃ for further reaction for 30min, then further heating to 100 ℃, degassing the solution for 10min, and removing the redundant methanol; finally in N2Further heating to 290 ℃ under protection, reacting for 90 min, stirring, cooling to room temperature, washing with ethanol and cyclohexane, centrifuging to obtain core nano product, and dispersing in cyclohexane solution for later use;
(2) preparing the nano particles with the core-shell structure: mixing Y (CH)3COO)3Adding into oleic acid and octadecylene, heating to 150 deg.C, reacting for 30min, and cooling to room temperature to obtain mixed solution; quickly adding the core nano product prepared in the step (1) into the mixed solution, heating to 80 ℃ for reaction for 30min, and removing cyclohexane; NaOH and NH are added4Heating the methanol solution of F to 50 ℃ for further reaction for 30min, then further heating to 100 ℃, degassing the solution for 10min, and removing the redundant methanol; finally in N2Further heating to 290 ℃ under protection, reacting for 90 min, stirring, cooling to room temperature, washing with ethanol and cyclohexane, centrifuging to obtain core-shell structured nano-particles UCNPs, and dispersing in cyclohexane solution for later use;
（3）UCNPs@mSiO2preparing a nano composite material: taking the UCNPs solution dispersed in cyclohexane in the step (2), adding CTAB and water, violently stirring in an oil bath kettle at 40 ℃ until the solution is clarified to remove cyclohexane to form UCNP-CTAB solution, adding the UCNP-CTAB solution into water, ethanol and NaOH solution, stirring and heating to 70 ℃, then adding TEOS for reaction for 10min, washing the synthesized solution with ethanol for three times, removing CTAB by an ion exchange method, and then carrying out vacuum drying to obtain UCNPs @ mSiO2A nanocomposite;
(4) MAX vacuum 60 ℃ overnight, MAX and PbX were mixed2Mixing in DMF, heating to 80 deg.C, and mixingWhich is dripped into UCNPs @ mSiO prepared in the step (3)2Fully soaking the nano composite material, violently stirring for 30min, and finally drying at 95 ℃ for 30min to obtain the perovskite lanthanide series composite nano material, wherein X is one or more of Cl, Br and I.
2. The process for the preparation of the perovskite lanthanide composite nanomaterial of claim 1, wherein: the total mole amount of the rare earth acetate mixture in the step (1) is 0.1-1 mmol, and the rare earth acetate mixture is composed of Y (CH)3CO2)3、Yb(CH3CO2)3、Tm (CH3CO2)3According to the molar ratio of 69: 30: 1 are mixed.
3. The process for the preparation of the perovskite lanthanide composite nanomaterial of claim 1, wherein: in the step (1), the ratio of the sodium hydroxide to the ammonium fluoride is 1: 1-2, the ratio of oleic acid to octadecene is 1: 1 to 10, NaOH and NH4The sum ratio of the volume of the methanol solution of the F to the volume of the mixture of the rare earth acetates, the oleic acid and the octadecene is 1-10: 1.
4. the process for the preparation of the perovskite lanthanide composite nanomaterial of claim 1, wherein: in the step (2), the ratio of the sodium hydroxide to the ammonium fluoride is 1: 1-2, the ratio of oleic acid to octadecene is 1: 1 to 10, NaOH and NH4Volume of methanol solution of F with Y (CH)3COO)3The volume sum ratio of oleic acid to octadecene is 1-10: 1, Y (CH)3COO)3The amount of the compound is 0.1 to 1 mmol.
5. A perovskite lanthanide composite nanomaterial prepared by the preparation method as described in any one of claims 1 to 4, wherein: the perovskite lanthanide series composite nano material is UCNPs @ mSiO2@MAPbX3Wherein X is one or more of Cl, Br and I.
6. The perovskite lanthanide composite nanomaterial of claim 5, wherein: the diameter range of the whole composite nano material particle is 106nm-122 nm; wherein the core size of UCNPs is 27 +/-2 nm, the lattice spacing is 3.2nm +/-0.02A, and the thickness of silicon dioxide is 30 +/-2 nm.
7. Use of the perovskite lanthanide composite nanomaterial as defined in any one of claims 5 to 6 in a broadband photodetector, wherein: by changing the type and content of halogen elements, the perovskite lanthanide series composite nano material is excited by X rays, near infrared light and ultraviolet light to obtain a 300-800 nm broadband spectrum.
8. The use of claim 7, wherein the perovskite lanthanide composite nanomaterial is used as a broadband detector for detecting ultraviolet, near infrared and X-rays to obtain a response curve.
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