阅读说明：本技术 一种非线性CsPbX3纳米晶玻璃的制备方法 (Nonlinear CsPbX3Preparation method of nanocrystalline glass ) 是由 金梦菲菲 梁晓娟 向卫东 于 2020-02-23 设计创作，主要内容包括：本发明公开了一种非线性CsPbX<Sub>3</Sub>纳米晶玻璃的制备方法,包括如下步骤：(1)按照物质的量份数称取以下原料：B<Sub>2</Sub>O<Sub>3</Sub>20-50份；ZnO 2-10份；SiO<Sub>2</Sub>5-50份；Al<Sub>2</Sub>O<Sub>3</Sub>1-10份；MgO 1-10份；Cs<Sub>2</Sub>CO<Sub>3</Sub>3-40份；PbCl<Sub>2</Sub>+PbBr<Sub>2</Sub>+PbI<Sub>2</Sub>+NaCl+NaBr+NaI＝9-45份,其中PbCl<Sub>2</Sub>、PbBr<Sub>2</Sub>、PbI<Sub>2</Sub>这三者的用量均不为0或者其中之一用量为0或者其中两种用量为0；当PbX<Sub>2</Sub>用量不为0时,需满足摩尔比PbX<Sub>2</Sub>：NaX＝1:2；(2)将各原料放入马弗炉中进行高温熔化；结束后将玻璃液倒入预热好的模具中,待玻璃成型后放入退火炉中退火处理；然后在保温炉中进行析晶热处理,使玻璃中析出尺寸为纳米级别并且分布均匀的晶相,然后降温得到CsPbX<Sub>3</Sub>纳米晶玻璃。本发明制得的CsPbX<Sub>3</Sub>纳米晶玻璃具有高非线性折射率。(The invention discloses a nonlinear CsPbX 3 The preparation method of the nanocrystalline glass comprises the following steps: (1) weighing the following raw materials in parts by weight: b is 2 O 3 20-50 parts; 2-10 parts of ZnO; SiO 2 2 5-50 parts; al (Al) 2 O 3 1-10 parts; 1-10 parts of MgO; cs 2 CO 3 3-40 parts; PbCl 2 +PbBr 2 +PbI 2 9-45 parts of NaCl, NaBr and NaI, wherein PbCl 2 、PbBr 2 、PbI 2 The dosage of the three components is not 0, or one of the dosage is 0, or two of the dosages are 0; when PbX is present 2 When the amount is not 0, the molar ratio of PbX is required to be satisfied 2 : NaX ═ 1: 2; (2) putting the raw materials into a muffle furnace for high-temperature melting; pouring the molten glass into a preheated mold after the end of the processPutting the formed glass into an annealing furnace for annealing treatment; then carrying out crystallization heat treatment in a heat preservation furnace to precipitate a crystal phase with nano-grade size and uniform distribution in the glass, and then cooling to obtain CsPbX 3 A nanocrystalline glass. The CsPbX prepared by the invention 3 Nanocrystalline glasses have a high nonlinear refractive index.)

1. Nonlinear CsPbX₃The preparation method of the nanocrystalline glass comprises the following steps:

(1) weighing the following raw materials in parts by weight:

B₂O₃20-50 parts;

2-10 parts of ZnO;

SiO₂5-50 parts;

Al₂O₃1-10 parts;

1-10 parts of MgO;

Cs₂CO₃3-40 parts;

PbCl₂+PbBr₂+PbI₂9-45 parts of NaCl, NaBr and NaI

Wherein PbCl₂、PbBr₂、PbI₂The dosage of the three components is not 0, or one of the dosage is 0, or two of the dosages are 0; when PbCl is present₂When the amount is not 0, it is necessarySatisfies the molar ratio of PbCl₂: 1:2 of NaCl; when PbBr is present₂When the dosage is not 0, the molar ratio of PbBr is required to be satisfied₂: NaBr is 1: 2; when PbI₂When the amount is not 0, PbI is required to be satisfied₂：NaI＝1:2；

(2) Putting the raw materials into a muffle furnace, heating to 1050-; pouring the glass liquid into a preheated mold after the end of the process, and putting the glass into an annealing furnace for annealing treatment after the glass is formed; then carrying out crystallization heat treatment in a heat preservation furnace at 470-530 ℃ for 3-20 hours to precipitate a crystal phase with nano-grade and uniform distribution in the glass, and then cooling to obtain CsPbX₃A nanocrystalline glass.

2. The method of claim 1, wherein: the molar percentage content of each raw material is as follows:

B₂O₃25-35％；

ZnO 5-10％；

SiO₂20-30％；

Al₂O₃1-5％；

MgO 1-5％；

Cs₂CO₃5-10％；

PbCl₂+PbBr₂+PbI₂+NaCl+NaBr+NaI＝20-27％。

3. the method of claim 1, wherein: the molar percentage content of each raw material is as follows: b is₂O₃31％；ZnO 8％；SiO₂23％；Al₂O₃3％；MgO 3％；Cs₂CO₃8％；PbCl₂+PbBr₂+PbI₂+NaCl+NaBr+NaI＝24％。

4. The method according to any one of claims 1 to 3, wherein: the CsPbX₃Is CsPbCl₃、CsPb(Cl/Br)₃、CsPbBr₃、CsPb(Br/I)₃Or CsPbI₃。

5. The method of claim 4, wherein: the CsPbX₃Is CsPbBr₃。

6. The method according to any one of claims 1 to 3 or 5, wherein: in the step (2), all the raw materials are put into a muffle furnace, heated to 1280 ℃ for 150 minutes and kept warm for 30 minutes.

7. The method according to any one of claims 1 to 3 or 5, wherein: in the step (2), the preheating temperature of the die is 250-500 ℃, the annealing temperature is 250-500 ℃, and the annealing time is 100-200 minutes.

8. The method of claim 7, wherein: the preheating temperature of the die is 350 ℃, the annealing temperature is 360 ℃, and the annealing time is 200 minutes.

9. The method according to any one of claims 1 to 3 or 5, wherein: the heat treatment temperature is 470-500 ℃, and the heat treatment time is 8-12 h.

10. The method of claim 9, wherein: the heat treatment temperature is 500 ℃, and the heat treatment time is 10 h.

(I) technical field

The invention belongs to the field of nonlinear optics, and particularly relates to CsPbX₃(X ═ Cl, Br, I) preparation method of nanocrystalline glass.

(II) background of the invention

The high non-linear refractive index has important significance for applying a novel laser protector. The rapid progress of laser technology now, even the emergence of laser weapons, brings urgent laser protection requirements. The development of a novel broadband, high-transmission and tunable laser protector is a research hotspot in recent years, and the research is mainly focused on materials with nonlinear optical limiting effect. In principle, materials having nonlinear optical limiting effects include a single type (materials having only one nonlinear optical effect) and a composite type (materials having two or more nonlinear optical effects). The appearance of perovskite materials brings new possibility to optical amplitude limiting materials. [ Songlin, Lichoff, nonlinear optical limiting technique and laser protection [ J ]]Physics, 1996,25(6):0-0.][ Sunli, Paiwang, Liuxiandong, et al³⁺-DopedTorosinate Glass% Ho doping³⁺Non-linear optical characteristics [ J ] of borosilicate glass]The Chinese rare earth journal 2009,027(001) 51-56.]

Because perovskite nanocrystals have excellent photoelectric properties, in recent years, fully inorganic CsPbX₃The research on (X ═ Cl/Br, Br) nanocrystals is vigorous. At present, the main focus is on the linear optics field of the lead cesium halide nanocrystals, such as the fields of solar cells, LEDs, lasers, etc., but these researches only focus on the thermal injection of the synthesized colloidal solution or single crystal, and the present market application is still in need of solving the stability problem. In 2015, Sun and Zeng et al synthesized 9nm CsPbBr by hot injection₃Nanocrystals, first observed at an input intensity of 20GW/cm by tapping a Z-scan fit curve²The large two-photon absorption section is approximately equal to 1.2 multiplied by 10 under the wavelength of 800nm⁵And (3) GM. Subsequently, our group synthesized CsPbCl by heat injection and anion exchange₃、 CsPbBr₃、CsPbI₃Colloidal nanocrystals, and nonlinear polarizabilities between them were compared. But instead of the other end of the tubeThe stability problem of nanocrystals has not yet been solved.

Shore Guangzhan Shao, Shengnan Liu, Ling Ding, Zelong Zhang, Weidong Xiaoang, Xiajuanan Liang_xCs_1-xPbBr₃NCsglassespossessingsuperopticalpropertiesandstability for white light emitting diodes.ChemicalEngineeringJournal375(2019)122031]Discloses a compound B₂O₃-ZnO-SiO₂As base glass K_xCs_1-xPbBr₃NCs glass, which solves K_xCs_{1- x}PbBr₃Stability problems of NCs and indicate that the glasses have good third-order nonlinear optical properties, and due to K⁺So that CsPbBr is introduced₃The third-order nonlinear optical properties of NCs glass are enhanced. But its non-linear refractive index still needs to be improved.

Disclosure of the invention

The present invention is directed to overcoming the disadvantages and drawbacks of the prior art, and to providing a CsPbX with a high non-linear refractive index₃A method for preparing nanocrystalline glass.

The technical scheme adopted by the invention is as follows:

nonlinear CsPbX₃The preparation method of the nanocrystalline glass comprises the following steps:

(1) weighing the following raw materials in parts by weight:

B₂O₃20-50 parts;

2-10 parts of ZnO;

SiO₂5-50 parts;

Al₂O₃1-10 parts;

1-10 parts of MgO;

Cs₂CO₃3-40 parts;

PbCl₂+PbBr₂+PbI₂9-45 parts of NaCl, NaBr and NaI

Wherein PbCl₂、PbBr₂、PbI₂The dosage of the three components is not 0, or one of the dosage is 0, or two of the dosages are 0; when PbCl is present₂The dosage is notAt 0, the molar ratio of PbCl is satisfied₂: 1:2 of NaCl; when PbBr is present₂When the dosage is not 0, the molar ratio of PbBr is required to be satisfied₂: NaBr is 1: 2; when PbI₂When the amount is not 0, PbI is required to be satisfied₂：NaI＝1:2；

(2) Putting the raw materials into a muffle furnace, heating to 1050-; pouring the glass liquid into a preheated mold after the end of the process, and putting the glass into an annealing furnace for annealing treatment after the glass is formed; then carrying out crystallization heat treatment in a heat preservation furnace at 470-530 ℃ for 3-20 hours to precipitate a crystal phase with nano-grade and uniform distribution in the glass, and then cooling to obtain CsPbX₃A nanocrystalline glass.

CsPbX of the present invention₃The nanocrystalline glass is required to have high nonlinear refractive index, has better transparency at the working wavelength, can be made into blocks with enough size and optical uniformity, and has stable physical and chemical properties, and based on the fact, B-Si-Zn-Al-Mg is selected as base glass.

Preferably, the molar percentage content of each raw material is as follows:

B₂O₃25-35％；

ZnO 5-10％；

SiO₂20-30％；

Al₂O₃1-5％；

MgO 1-5％；

Cs₂CO₃5-10％；

PbCl₂+PbBr₂+PbI₂+NaCl+NaBr+NaI＝20-27％。

further preferably, the molar percentage content of each raw material is as follows: b is₂O₃31％；ZnO 8％；SiO₂23％；Al₂O₃3％；MgO 3％；Cs₂CO₃8％；PbCl₂+PbBr₂+PbI₂+NaCl+NaBr+NaI＝24％。

Preferably, the CsPbX is₃Is CsPbCl₃、CsPb(Cl/Br)₃、CsPbBr₃、CsPb(Br/I)₃Or CsPbI₃. Optimization ofSelecting the CsPbX₃Is CsPbBr₃。

Preferably, in step (2), each raw material is put into a muffle furnace, heated to 1280 ℃ for 150 minutes, and then kept at that temperature for 30 minutes.

Preferably, in the step (2), the preheating temperature of the mold is 250-500 ℃, the annealing temperature is 250-500 ℃, and the annealing time is 100-200 minutes. Further preferably, the preheating temperature of the mold is 350 ℃, the annealing temperature is 360 ℃, and the annealing time is 200 minutes.

Preferably, the heat treatment temperature is 470-500 ℃, and the heat treatment time is 8-12 h; most preferably, the heat treatment temperature is 500 ℃ and the heat treatment time is 10 hours.

The invention discovers CsPbX through 4f phase coherent imaging (NIT-PO) and Z-Scan test₃The nanocrystalline glass exhibits good third-order nonlinear properties, especially a high nonlinear refractive index. In particular CsPbBr₃The nanocrystalline glass not only has very high nonlinear refractive index, but also has rare reverse saturable absorption performance, and tests with 4f phase coherent imaging (NIT-PO) show self-defocusing reverse saturable absorption at 532nm, and tests with Z-Scan show self-focusing reverse saturable absorption at 800 nm.

The CsPbX prepared by the traditional melting heat treatment method is utilized in the invention₃The nanocrystalline glass is particularly suitable for preparing a laser protector due to the high nonlinear refractive index of the nanocrystalline glass.

Compared with the prior art, the invention has the advantages and effects that:

(1) the CsPbX can be obtained by simple high-temperature melting and in-situ crystallization₃Compared with the thermal injection of colloidal solution and single crystal (as shown in table 2), the microcrystalline glass has the advantages of convenient synthesis method, convenient transportation, strong stability and benefit for practical application.

(2) The CsPbX with high nonlinear refractive index is obtained by selecting specific base glass and adjusting the crystallization temperature and the halogen ratio₃Microcrystalline glass.

(IV) description of the drawings

FIG. 1: (a) is the glass fraction of ClBrA, ClBrB and CPB NCsX-ray diffraction patterns at 470 deg.C, 500 deg.C and 530 deg.C for 10h, respectively. Furthermore, CsPbBr₃The standard cubic crystal structure of (PDF #54-0752) is also shown; (b) are ClBrA, ClBrB and CPB NCs glass samples of different heat treatment temperatures, at the same temperature, the left column is the sample in sunlight and the right column is the corresponding sample in uv.

FIG. 2: (a) - (d) Transmission Electron Microscopy (TEM) images of ClBrA, ClBrB and CPB NCs glasses, respectively. (e) - (h) HRTEM images of ClBrA, ClBrB and CPB NCs glasses, respectively. (i) The- (k) EDS element spectra of the CPB NCs glasses obtained by heat treatment at 500 ℃ for 10 hours, respectively. (l) Is the crystal structure of CPB NCs.

FIG. 3: (a) and (c) transmission electron microscope images of ClBrA and ClBrBNCs glasses, respectively, heat treated at 470 ℃. (b) And (d) HRTEM images of ClBrA and ClBrBNCs glasses, respectively, heat treated at 470 ℃. Thermal imaging of ClBrA (b) and ClBrB (d) NCs glasses. (e) And (f) EDS diagrams for ClBrA and ClBrB NCs glasses, respectively, heat treated at 500 ℃.

FIG. 4: (a) - (f) are CsPbX, respectively₃Size distribution histogram of NCs glass.

FIG. 5: (a) PL emission spectra of ClBrA, ClBrB and CPB NCs glasses with different heat treatment temperatures; (b) is an ultraviolet-visible absorption spectrum chart of ClBrA, ClBrB and CPB NCs glass with different heat treatment temperatures; (c) is ClBrA, ClBrB and CPB NCs glasses at different heat treatment temperatures (alpha h v)²A spectrogram plotted under- (h ν).

FIG. 6 is a NIT-PO test chart in which (a), (c), (e), (g), (i), (k) show experimental nonlinear images; (b) the corresponding data simulation results are shown in (d), (f), (h), (j), (l).

FIG. 7: thermal stability cycle plots for ClBrA, ClBrB and CPB NCs glasses obtained with heat treatment at 500 ℃ for 10 hours.

FIG. 8: (a) and (b) and (c) are photographs taken under ultraviolet rays after immersing the glass ClBrA, ClBrB and CPBNCs, which are obtained by heat treatment at 500 ℃ for 10 hours, in water for various times (from left to right: 0 day, 5 days, 10 days, 15 days, 30 days, 60 days and 75 days), respectively.

FIG. 9: (a) is XRD patterns of CPB NCs glass obtained by heat treatment for 10 hours at 470 ℃ before radiation, after radiation and after annealing; (b) is the 3DPL spectrum of CPB NCs glass obtained by heat treatment at 470 ℃ for 10h before irradiation, after irradiation and after annealing. Clearly, there is no change in the fluorescence peak and intensity before and after laser irradiation.

FIG. 10: (a) - (c) are photographs of the CPB NCs glass heat-treated at 470 ℃ for 10 hours before irradiation, after irradiation and after annealing, respectively, the white background being taken under normal light and the black background being taken at 365 nm; (e) in the integrating sphere, a 460nm laser irradiates a sample for the first time; (f) in the integrating sphere, 460nm laser irradiates a sample for the second time; (g) and (h) is the emission spectrum of CPB NCs glass heat-treated at 470 ℃ for 10h at different laser powers.

(V) detailed description of the preferred embodiments

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.

The raw materials used in the embodiment of the invention are as follows: silicon dioxide (SiO)₂99.9%), boron oxide (B)₂O₃99.9%), alumina (Al)₂O₃99.99%), magnesium oxide (MgO, 99.99%), zinc oxide (ZnO, 99%), cesium carbonate (Cs)₂CO₃99%), lead bromide (PbBr)₂99%), lead chloride (PbCl)₂99%). Sodium bromide (NaBr, 99.9%), sodium chloride (NaCl, 99.99%) were obtained from alatin. All chemicals were used directly.