阅读说明：本技术 Pvb包覆纳米晶玻璃薄膜的制备和应用 (Preparation and application of PVB (polyvinyl butyral) coated nanocrystalline glass film ) 是由 向卫东 梅恩柔 柳建明 梁晓娟 于 2021-07-30 设计创作，主要内容包括：本发明公开了一种PVB包覆CsPbCl-(2)Br/CsPbBr-(3)/CsPbBrI-(2)纳米晶玻璃粉薄膜材料的制备和应用。所述制备方法包括如下步骤：(1)制备CsPbCl-(2)Br纳米晶玻璃；(2)制备CsPbBr-(3)纳米晶玻璃；(3)制备CsPbBrI-(2)纳米晶玻璃；(4)合成PVB包覆CsPbCl-(2)Br/CsPbBr-(3)/CsPbBrI-(2)纳米晶玻璃粉薄膜材料。本发明提供了所述制备方法制得的薄膜材料在制备白光LED中的应用。本发明制得的PVB@CsPbCl-(2)Br/CsPbBr-(3)/CsPbBrI-(2)纳米晶玻璃薄膜材料具有薄、水稳定性好、直接发出白光且光学性能优异的性能,其制备的白光LED色温低、显色指数高、光效高,具有优异的光学性能。(The invention discloses a PVB coated CsPbCl 2 Br/CsPbBr 3 /CsPbBrI 2 Preparation and application of the nanocrystalline glass powder film material. The preparation method comprises the following steps: (1) preparation of CsPbCl 2 Br nanocrystalline glass; (2) preparation of CsPbBr 3 Nanocrystalline glass; (3) preparation of CsPbBrI 2 Nanocrystalline glass; (4) synthetic PVB coated CsPbCl 2 Br/CsPbBr 3 /CsPbBrI 2 A nanocrystalline glass powder film material. The invention provides application of the thin film material prepared by the preparation method in preparing a white light LED. PVB @ CsPbCl prepared by the invention 2 Br/CsPbBr 3 /CsPbBrI 2 The nanocrystalline glass film material has the advantages of thinness, good water stability, capability of directly emitting white light and excellent optical performance, and the white light LED prepared from the nanocrystalline glass film material has low color temperature, high color rendering index, high light efficiency and excellent optical performance.)

1. PVB cladding CsPbCl₂Br/CsPbBr₃/CsPbBrI₂The preparation method of the nanocrystalline glass powder film material comprises the following steps:

(1)CsPbCl₂preparation of Br nanocrystalline glass

Weighing the following raw materials in percentage by mole: b is₂O₃22.5％，SiO₂37％，ZnO 10.2％，Cs₂CO₃16.5％，PbBr₂1.2％，PbCl₂2.4 percent of NaBr, 3.4 percent of NaBr and 6.8 percent of NaCl; mixing the raw materialsUniformly mixing and grinding, heating to 1200-1300 ℃, preserving heat for 10-15 minutes, pouring the mixture onto a cast iron mold with the temperature set at the glass transition temperature, then placing the mixture into a high-temperature furnace, preserving heat for 3-6 hours at the glass transition temperature for annealing, cooling to a certain temperature along with the furnace, closing a power supply of the high-temperature furnace, automatically cooling to room temperature, taking out glass, and obtaining CsPbCl₂Br nanocrystalline glass, then grind into powder;

(2)CsPbBr₃preparation of nanocrystalline glass

Weighing the following raw materials in percentage by mole: b is₂O₃22.5％，SiO₂37％，ZnO 10.2％，Cs₂CO₃16.5％，PbBr₂3.3 percent of NaBr, 10.5 percent of NaBr; mixing and grinding the raw materials uniformly, heating to 1200-1300 ℃, preserving heat for 10-15 minutes, pouring the mixture onto a cast iron mold with the temperature set at the glass transition temperature, then placing the cast iron mold into a high-temperature furnace, preserving heat for 3-6 hours at the glass transition temperature for annealing, then cooling to a certain temperature along with the furnace, closing a power supply of the high-temperature furnace, automatically cooling to room temperature, taking out the glass, and obtaining CsPbBr₃Nanocrystalline glass is ground into powder;

(3)CsPbBrI₂preparation of nanocrystalline glass

Weighing the following raw materials in percentage by mole: b is₂O₃22.5％，SiO₂37％，ZnO 10.2％，Cs₂CO₃16.5％，PbBr₂1.2％，PbI₂2.4 percent of NaBr, 3.4 percent of NaI and 6.8 percent of NaI; mixing and grinding the raw materials uniformly, heating to 1200-1300 ℃, preserving heat for 10-15 minutes, pouring the mixture onto a cast iron mold with the temperature set at the glass transition temperature, then placing the cast iron mold in a high-temperature furnace for annealing, preserving heat for 3-6 hours at the glass transition temperature, then cooling to a certain temperature along with the furnace, closing a power supply of the high-temperature furnace, automatically cooling to room temperature, taking out the glass, and obtaining CsPbBrI₂Nanocrystalline glass is ground into powder;

(4) PVB coated CsPbCl₂Br/CsPbBr₃/CsPbBrI₂Synthesis of nano-crystal glass powder film

Mixing PVB with chloroform solvent to form a gel, and immediately mixing the gel with the CsPbCl prepared in the step (1)₂Br nano crystal glass powder,CsPbBr prepared in step (2)₃Nanocrystalline glass powder and CsPbBrI prepared in step (3)₂Mixing and stirring the nanocrystalline glass powder in proportion, pouring the mixture into a film forming container, placing the container into an oven for 1 to 2 hours, volatilizing the solvent to form a composite film, and obtaining the PVB coated CsPbCl₂Br/CsPbBr₃/CsPbBrI₂A nanocrystalline glass film material; PVB, chloroform solvent and CsPbCl₂Br/CsPbBr₃/CsPbBrI₂The mass ratio of the nanocrystalline glass powder is 0.25 g: 4.5 mL: (0.2g/0.27g/0.15 g).

2. The method of claim 1, wherein: in the steps (1) - (3), the raw materials are mixed and ground uniformly, then the temperature is raised to 1200 ℃, and the temperature is kept for 10 minutes.

3. The method of claim 1, wherein: in steps (1) to (3), the temperature is maintained at the glass transition temperature for 3 hours.

4. The PVB-coated CsPbCl prepared by the process of claim 1₂Br/CsPbBr₃/CsPbBrI₂The application of the nanocrystalline glass film material in preparing a white light LED.

5. The use according to claim 4, characterized in that said use is: coating the PVB with CsPbCl₂Br/CsPbBr₃/CsPbBrI₂And placing the nanocrystalline glass film on a 365nm purple light chip to manufacture the white light LED.

Technical Field

The invention belongs to the field of perovskite nanocrystalline glass films, and particularly relates to PVB (polyvinyl butyral) coated CsPbCl₂Br/CsPbBr₃/CsPbBrI₂A preparation method of a nanocrystalline glass film material and application thereof in preparing a white light LED.

Background

All-inorganic CsPbX₃(X ═ Cl, Br, I) nanocrystals are widely used in various fields such as Light Emitting Diodes (LEDs), photodetection, laser, and bio-imaging due to tunable emission wavelength, high quantum efficiency, and narrow half-peak width. Although CsPbX₃The nanocrystalline has the advantages, but the problem of poor stability seriously hinders the practical application of the nanocrystalline, namely CsPbX₃The luminescent properties of nanocrystals can rapidly decrease when exposed to atmospheric water vapor. To overcome this problem, CsPbX was used₃The problem of poor stability of nanocrystals embedded in glass can be greatly improved, and CsPbX can be formed by using a thin film₃The CsPbX is further improved by coating the nanocrystalline glass₃Stability of the nanocrystals.

Disclosure of Invention

It is a first object of the present invention to overcome the disadvantages and drawbacks of the prior art by providing a PVB coated CsPbCl₂Br/CsPbBr₃/CsPbBrI₂The preparation method of the nanocrystalline glass powder film material realizes the direct emission of white light in a PVB film and obtains excellent optical performance.

It is a second object of the present invention to provide such PVB-coated CsPbCl₂Br/CsPbBr₃/CsPbBrI₂The application of the nanocrystalline glass powder film material in the preparation of white light LEDs has excellent optical performance.

In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:

in a first aspect, the invention provides a PVB-coated CsPbCl₂Br/CsPbBr₃/CsPbBrI₂The preparation method of the nanocrystalline glass powder film material comprises the following steps:

(1)CsPbCl₂preparation of Br nanocrystalline glass

Weighing the following raw materials in percentage by mole: b is₂O₃22.5％，SiO₂37％，ZnO 10.2％，Cs₂CO₃16.5％，PbBr₂1.2％，PbCl₂2.4 percent of NaBr, 3.4 percent of NaBr and 6.8 percent of NaCl; uniformly mixing and grinding the raw materials, heating to 1200-1300 ℃, preserving heat for 10-15 minutes, pouring the mixture onto a cast iron mold with the temperature set at the glass transition temperature (Tg), then placing the cast iron mold into a high-temperature furnace, preserving heat for 3-6 hours at the glass transition temperature (Tg) for annealing, cooling to a certain temperature (such as 30 ℃) along with the furnace, turning off a power supply of the high-temperature furnace, automatically cooling to room temperature, taking out glass, and obtaining CsPbCl₂Br nanocrystalline glass, then grind into powder;

(2)CsPbBr₃preparation of nanocrystalline glass

Weighing the following raw materials in percentage by mole: b is₂O₃22.5％，SiO₂37％，ZnO 10.2％，Cs₂CO₃16.5％，PbBr₂3.3 percent of NaBr, 10.5 percent of NaBr; uniformly mixing and grinding the raw materials, heating to 1200-1300 ℃, preserving heat for 10-15 minutes, pouring the mixture onto a cast iron mold with the temperature set at the glass transition temperature (Tg), then placing the cast iron mold into a high-temperature furnace, preserving heat for 3-6 hours at the glass transition temperature (Tg) for annealing, cooling to a certain temperature (such as 30 ℃) along with the furnace, turning off a power supply of the high-temperature furnace, automatically cooling to room temperature, taking out glass, and obtaining CsPbBr₃Nanocrystalline glass is ground into powder;

(3)CsPbBrI₂preparation of nanocrystalline glass

Weighing the following raw materials in percentage by mole: b is₂O₃22.5％，SiO₂37％，ZnO 10.2％，Cs₂CO₃16.5％，PbBr₂1.2％，PbI₂2.4 percent of NaBr, 3.4 percent of NaI and 6.8 percent of NaI; mixing and grinding the raw materials uniformly, heating to 1200-1300 ℃, preserving heat for 10-15 minutes, pouring the mixture onto a cast iron mold with the temperature set at the glass transition temperature (Tg), then placing the cast iron mold into a high-temperature furnace for annealing, preserving heat for 3-6 hours at the glass transition temperature (Tg), and then carrying out annealing treatment on the mixtureCooling to a certain temperature (such as 30 ℃) along with the furnace, closing the power supply of the high-temperature furnace, automatically cooling to room temperature, taking out glass, and obtaining the CsPbBrI₂Nanocrystalline glass is ground into powder;

(4) PVB coated CsPbCl₂Br/CsPbBr₃/CsPbBrI₂Synthesis of nano-crystal glass powder film

Mixing PVB with chloroform solvent to form a gel, and immediately mixing the gel with the CsPbCl prepared in the step (1)₂Br nanocrystalline glass powder and CsPbBr prepared in step (2)₃Nanocrystalline glass powder and CsPbBrI prepared in step (3)₂Mixing and stirring the nanocrystalline glass powder in proportion, pouring the mixture into a film forming container, placing the container into an oven for 1 to 2 hours, volatilizing the solvent to form a composite film, and obtaining the PVB coated CsPbCl₂Br/CsPbBr₃/CsPbBrI₂A nanocrystalline glass film material; PVB, chloroform solvent and CsPbCl₂Br/CsPbBr₃/CsPbBrI₂The mass ratio of the nanocrystalline glass powder is 0.25 g: 4.5 mL: (0.2g/0.27g/0.15 g).

Preferably, in steps (1) to (3), the raw materials are mixed and ground uniformly, and then heated to 1200 ℃ and kept warm for 10 minutes.

Preferably, in steps (1) to (3), the temperature is maintained at the glass transition temperature (Tg temperature) for 3 hours. In the present invention, the "glass transition temperature (Tg temperature)" can be measured according to a conventional method.

The PVB coated CsPbCl prepared by the invention₂Br/CsPbBr₃/CsPbBrI₂The shape of the nanocrystalline glass film material may be planar, concave, convex.

PVB coated CsPbCl prepared by the invention₂Br/CsPbBr₃/CsPbBrI₂The nanocrystalline glass film emits white light, has good optical performance, and can be directly applied to a white light LED.

In a second aspect, the invention provides the PVB-coated CsPbCl₂Br/CsPbBr₃/CsPbBrI₂The application of the nanocrystalline glass film in the preparation of white light LEDs.

Specifically, the application is as follows: coating the PVB with CsPbCl₂Br/CsPbBr₃/CsPbBrI₂And placing the nanocrystalline glass film on a 365nm purple light chip to manufacture the white light LED.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention researches a coated CsPbCl with simple process and low cost₂Br/CsPbBr₃/CsPbBrI₂Nano-crystalline glass method and PVB @ CsPbCl prepared by nano-crystalline glass method₂Br/CsPbBr₃/CsPbBrI₂The nanocrystalline glass film material has the properties of thinness, good water stability, direct white light emission and excellent optical performance.

(2) The PVB @ CsPbCl is utilized in the invention₂Br/CsPbBr₃/CsPbBrI₂The white light LED prepared from the nanocrystalline glass film material has the advantages of low color temperature, high color rendering index, high luminous efficiency and excellent optical performance.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.

FIG. 1 shows CsPbCl respectively coated with PVB prepared in examples 1-5₂Br/CsPbBr₃/CsPbBrI₂Fluorescence plot of nanocrystalline glass film.

FIG. 2 is a PVB coated CsPbCl prepared in example 3₂Br/CsPbBr₃/CsPbBrI₂Water stability profile of nanocrystalline glass films.

FIG. 3 is a PVB coated CsPbCl prepared in example 3₂Br/CsPbBr₃/CsPbBrI₂And (3) a white light LED spectrum prepared from the nanocrystalline glass film.

Detailed Description

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.

Examples 1 to 5

(1)CsPbCl₂Preparation of Br nanocrystalline glass

Weighing the raw materials according to the following mol percentage, and mixing and grinding uniformly: the molar percentage content of the raw materials is as follows: b is₂O₃22.5％，SiO₂37％，ZnO 10.2％，Cs₂CO₃16.5％，PbBr₂1.2％，PbCl₂2.4 percent of NaBr, 3.4 percent of NaBr and 6.8 percent of NaCl; heating the mixed raw materials to 1200 ℃, preserving heat for 10 minutes, pouring the mixture onto a cast iron mold, then placing the cast iron mold in a high-temperature furnace for annealing, preserving heat for 3 hours at the glass transition temperature Tg, then cooling the glass to 30 ℃ along with the furnace, closing a power supply of the high-temperature furnace, automatically cooling the glass to room temperature, and taking out the glass to obtain CsPbCl₂Br nanocrystalline glass.

(2)CsPbBr₃Preparation of nanocrystalline glass

Weighing the raw materials according to the following mol percentage, and mixing and grinding uniformly: the molar percentage content of the raw materials is as follows: b is₂O₃22.5％，SiO₂37％，ZnO 10.2％，Cs₂CO₃16.5％，PbBr₂3.3 percent of NaBr, 10.5 percent of NaBr; heating the mixed raw materials to 1200 ℃, preserving heat for 10 minutes, pouring the mixture onto a cast iron mold, then placing the cast iron mold in a high-temperature furnace for annealing, preserving heat for 3 hours at the glass transition temperature Tg, then cooling the glass to 30 ℃ along with the furnace, closing a power supply of the high-temperature furnace, automatically cooling the glass to room temperature, and taking out the glass to obtain CsPbBr₃A nanocrystalline glass.

(3)CsPbBrI₂Preparation of nanocrystalline glass

Weighing the raw materials according to the following mol percentage, and mixing and grinding uniformly: the molar percentage content of the raw materials is as follows: b is₂O₃22.5％，SiO₂37％，ZnO 10.2％，Cs₂CO₃16.5％，PbBr₂1.2％，PbI₂2.4 percent of NaBr, 3.4 percent of NaI and 6.8 percent of NaI; heating the mixed raw materials to 1200 ℃, preserving heat for 10 minutes, pouring the mixture onto a cast iron mold, then placing the cast iron mold in a high-temperature furnace for annealing, preserving heat for 3 hours at the glass transition temperature Tg, then cooling the glass to 30 ℃ along with the furnace, turning off a power supply of the high-temperature furnace, automatically cooling the glass to room temperature, and taking out the glass to obtain CsPbBrI₂Nanocrystalline glassGlass.

(4) PVB coated CsPbCl₂Br/CsPbBr₃/CsPbBrI₂Synthesis of nano-crystal glass powder film

0.25g of PVB was mixed with 4.5ml of chloroform and dissolved in a gel, which was immediately mixed with CsPbCl prepared in steps (1), (2) and (3)₂Br/CsPbBr₃/CsPbBrI₂Mixing and stirring the nanocrystalline glass powder according to the proportion in the table 1, pouring the mixture into a film forming container, putting the container into a 45 ℃ oven, standing for 2 hours, and volatilizing the solvent to form a composite film with the thickness of 0.15 mm.

The PVB prepared in examples 1-5 was coated with CsPbCl₂Br/CsPbBr₃/CsPbBrI₂And (3) placing the nanocrystalline glass film on a 365nm purple light chip to manufacture the LED. In addition, opaque silicone gel was filled at the edges of the device to prevent leakage of violet light. See if white light is emitted. The results show that only the film prepared in example 3 can emit white light. The white LED in example 3 had the following properties:

color coordinates (0.3032, 0.2898); color temperature: 7721 k; color rendering index: 18.4 of the total weight of the mixture; light efficiency: 12.25 lm/W.

TABLE 1 EXAMPLES 1-5 amounts of materials added to the respective raw materials, finished products and quantums of the finished products

Comparative example 1

CsPbCl₂Br/CsPbBr₃/CsPbBrI₂The procedure for the preparation of nanocrystalline glass was the same as in example 3.

0.25g PVB was mixed with 4.5mL toluene solvent and immediately thereafter with 0.2g/0.27g/0.15g CsPbCl₂Br/CsPbBr₃/CsPbBrI₂Mixing and stirring the nanocrystalline glass powder, pouring the mixture into a watch glass, putting the watch glass into an oven at 45 ℃ for 1-2 hours, and observing that the film cannot be formed.

Comparative example 2

Referring to example 3, only with the difference that the amount of chloroform solvent was 3mL, no film formation was observed.

Comparative example 3

Referring to example 3, except that the amount of chloroform solvent was 6mL, whitening of the film was observed, which was not favorable for the preparation of a high-quality film.

Comparative example 4

(1)CsPbCl₂Preparation of Br nanocrystalline glass

Weighing the raw materials according to the following mol percentage, and mixing and grinding uniformly: the molar percentage content of the raw materials is as follows: p₂O₅22.5％，SiO₂37％，ZnO 10.2％，Cs₂CO₃16.5％，PbBr₂1.2％，PbCl₂2.4 percent of NaBr, 3.4 percent of NaBr and 6.8 percent of NaCl; heating the mixed raw materials to 1200 ℃, preserving heat for 10 minutes, pouring the mixture onto a cast iron mold, then placing the cast iron mold in a high-temperature furnace for annealing, preserving heat for 3 hours at the glass transition temperature Tg, then cooling the glass to 30 ℃ along with the furnace, closing a power supply of the high-temperature furnace, automatically cooling the glass to room temperature, and taking out the glass to obtain CsPbCl₂Br nanocrystalline glass.

(2)CsPbBr₃Preparation of nanocrystalline glass

Weighing the raw materials according to the following mol percentage, and mixing and grinding uniformly: the molar percentage content of the raw materials is as follows: p₂O₅22.5％，SiO₂37％，ZnO 10.2％，Cs₂CO₃16.5％，PbBr₂3.3 percent of NaBr, 10.5 percent of NaBr; heating the mixed raw materials to 1200 ℃, preserving heat for 10 minutes, pouring the mixture onto a cast iron mold, then placing the cast iron mold in a high-temperature furnace for annealing, preserving heat for 3 hours at the glass transition temperature Tg, then cooling the glass to 30 ℃ along with the furnace, closing a power supply of the high-temperature furnace, automatically cooling the glass to room temperature, and taking out the glass to obtain CsPbBr₃A nanocrystalline glass.

(3)CsPbBrI₂Preparation of nanocrystalline glass

Weighing the raw materials according to the following mol percentage, and mixing and grinding uniformly: the molar percentage content of the raw materials is as follows: p₂O₅22.5％，SiO₂37％，ZnO 10.2％，Cs₂CO₃16.5％，PbBr₂1.2％，PbI₂2.4 percent of NaBr, 3.4 percent of NaI and 6.8 percent of NaI; heating the mixed raw materials to 1200 ℃, preserving the heat for 10 minutes, pouring the mixture onto a cast iron mold, and then putting the cast iron mold into a high-temperature furnace to feedAnnealing, keeping the temperature at the glass transition temperature Tg for 3 hours, then cooling to 30 ℃ along with the furnace, turning off the power supply of the high-temperature furnace, automatically cooling to room temperature, and taking out the glass to obtain CsPbBrI₂A nanocrystalline glass.

(4) PVB coated CsPbCl₂Br/CsPbBr₃/CsPbBrI₂Synthesis of nano-crystal glass powder film

0.25g of PVB was mixed with 4.5ml of chloroform and dissolved in a gel, which was immediately mixed with CsPbCl prepared in steps (1), (2) and (3)₂Br/CsPbBr₃/CsPbBrI₂Mixing and stirring the nano-crystalline glass powder according to the proportion of 0.18g/0.25g/0.13g, pouring the mixture into a film forming container, putting the container into a baking oven at the temperature of 45 ℃ for 2 hours, and volatilizing the solvent to form a composite film with the thickness of 0.15 mm.

The PVB prepared in the comparative example was coated with CsPbCl₂Br/CsPbBr₃/CsPbBrI₂And (3) placing the nanocrystalline glass film on a 365nm purple light chip to manufacture the LED. In addition, opaque silicone gel was filled at the edges of the device to prevent leakage of violet light. See if white light is emitted. The results show that the film prepared in the comparative example did not exhibit the same property of emitting white light as example 3. The white LED in the comparative example had the following properties:

color coordinates (0.2976, 0.3017); color temperature: 7886 k; color rendering index: 12.2; light efficiency: 7.26 lm/W.

The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.