DIVALENT MANGANESE-DOPED ALL-INORGANIC PEROVSKITE QUANTUM DOT GLASS AND PREPARATION METHOD THEREOF

Abstract

The present invention relates to a divalent manganese-doped all-inorganic perovskite quantum dot glass, and constituents of the divalent manganese-doped all-inorganic perovskite quantum dot glass are as follows: B.sub.2O.sub.3: 25%-45%, SiO.sub.2: 25%-45%, MCO.sub.3: 1%-10%, Al.sub.2O.sub.3: 1%-10%, ZnO: 1%-5%, Cs.sub.2CO.sub.3: 1%-10%, PbCl.sub.2: 1%-10%, NaCl: 1%-10%, MnCl.sub.2: 1%-10%, wherein M is Ca, Sr or Ba. Preparation of the quantum dot glass is as follows: grinding each raw constituent materials and mixing well to form a mixture, melting the mixture, followed by molding, annealing and performing thermal treatment. By the thermal treatment at different temperatures, a divalent manganese-doped quantum dot glass can be obtained. The divalent manganese ions doped perovskite quantum dot glass is a kind of light-emitting material with great application prospect, for possessing good stability and rather high fluorescence quantum yield.

Claims

1. A divalent manganese-doped all-inorganic perovskite quantum dot glass, wherein by molar percentage, constituents of the divalent manganese-doped all-inorganic perovskite quantum dot glass are as follows: B.sub.2O.sub.3: 25%-45%, SiO.sub.2: 25%-45%, MCO.sub.3: 1%-10%, Al.sub.2O.sub.3: 1%-10%, ZnO: 1%-5%, Cs.sub.2CO.sub.3: 1%-10%, PbCl.sub.2: 1%-10%, NaCl: 1%-10%, MnCl.sub.2: 1%-10%.

2. The divalent manganese-doped all-inorganic perovskite quantum dot glass according to claim 1, wherein by molar percentage, constituents of the divalent manganese-doped all-inorganic perovskite quantum dot glass are as follows: B.sub.2O.sub.3: 30%-40%, SiO.sub.2: 30%-40%, MCO.sub.3: 1%-10%, Al.sub.2O.sub.3: 1%-10%, ZnO: 1%-5%, Cs.sub.2CO.sub.3: 1%-10%, PbCl.sub.2: 1%-10%, NaCl: 1%-10%, MnCl.sub.2: 1%-10%.

3. The divalent manganese-doped all-inorganic perovskite quantum dot glass according to claim 1, wherein a molar ratio of MnCl.sub.2 to PbCl.sub.2 is more than 3:7 and less than 7:3.

4. The divalent manganese-doped all-inorganic perovskite quantum dot glass according to claim 1, wherein a sum of the molar percentages of MCO.sub.3 and ZnO accounts for less than 10% of a total constituent of the glass.

5. A preparation method of the divalent manganese-doped all-inorganic perovskite quantum dot glass according to claim 1, wherein the preparation method comprises the following steps: S1: grinding each constituent raw materials and mixing well, placing in a sealed container, performing melting treatment for a period of time t1 at a temperature of T1 in a reducing atmosphere, followed by molding, and annealing to obtain a transparent glass; and S2: performing thermal treatment of the transparent glass obtained in S1 for a period of time t2 at a temperature of T2, then cooling to room temperature to obtain the divalent manganese-doped all-inorganic perovskite quantum dot glass; the temperature T1 of the melting treatment in S1 ranges between 1200 C. and 1400 C., and the period of time t1 of the melting treatment is 10 minutes to 60 minutes; the temperature T2 of the thermal treatment in S2 is 360 C. to 600 C., and the period of time t2 of the thermal treatment is 4 hours to 20 hours.

6. A method of preparing luminescent materials using the divalent manganese-doped all-inorganic perovskite quantum dot glass according to claim 1.

7. The method according to claim 6, wherein the divalent manganese-doped all-inorganic perovskite quantum dot glass is used as an optical conversion material in fields of white LED, plant-growth lighting and solar cells.

8. The divalent manganese-doped all-inorganic perovskite quantum dot glass according to claim 2, wherein a molar ratio of MnCl.sub.2 to PbCl.sub.2 is more than 3:7 and less than 7:3.

9. A method of preparing luminescent materials using the divalent manganese-doped all-inorganic perovskite quantum dot glass according to claim 8.

10. The method according to claim 9, wherein the divalent manganese-doped all-inorganic perovskite quantum dot glass is used as an optical conversion material in fields of white LED, plant-growth lighting and solar cells.

11. A method of preparing luminescent materials using the divalent manganese-doped all-inorganic perovskite quantum dot glass according to claim 2.

12. The method according to claim 11, wherein the divalent manganese-doped all-inorganic perovskite quantum dot glass is used as an optical conversion material in fields of white LED, plant-growth lighting and solar cells.

13. A method of preparing luminescent materials using the divalent manganese-doped all-inorganic perovskite quantum dot glass according to claim 3.

14. The method according to claim 13, wherein the divalent manganese-doped all-inorganic perovskite quantum dot glass is used as an optical conversion material in fields of white LED, plant-growth lighting and solar cells.

15. A method of preparing luminescent materials using the divalent manganese-doped all-inorganic perovskite quantum dot glass according to claim 4.

16. The method according to claim 15, wherein the divalent manganese-doped all-inorganic perovskite quantum dot glass is used as an optical conversion material in fields of white LED, plant-growth lighting and solar cells.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0021] FIG. 1 is an XRD diagram of a Mn.sup.2+-doped all-inorganic perovskite quantum dot glass prepared by thermal treatment at 500 C. for 10 hours in Example 1.

[0022] FIG. 2 is a TEM diagram of a Mn.sup.2+-doped all-inorganic perovskite quantum dot glass prepared by thermal treatment at 515 C. for 15 hours in Example 2.

[0023] FIG. 3 is an absorption spectrum of a Mn.sup.2+-doped all-inorganic perovskite quantum dot glass prepared by thermal treatment at 520 C. for 20 hours in Example 3.

[0024] FIG. 4 shows pictures of a product in ambient and under 365 nm and excitation emission spectrum of a Mn.sup.2+-doped all-inorganic perovskite quantum dot glass prepared by thermal treatment at 530 C. for 10 hours in Example 4.

[0025] FIG. 5 is a lifetime curve of a Mn.sup.2+-doped all-inorganic perovskite quantum dot glass prepared by thermal treatment at 530 C. for 20 hours in Example 5.

[0026] FIG. 6 shows excitation and emission spectrum of a divalent manganese-doped all-inorganic perovskite quantum dot glass synthesized by thermal treatment at 530 C. for 15 hours in the comparative example 1.

DESCRIPTION OF THE EMBODIMENTS

[0027] The present invention is further described by specific examples and accompanied drawings, but the examples do not limit the present invention in any ways. Unless specified, reagents, methods and devices used in the present invention are conventional reagents, methods and devices in the art.

[0028] Unless specified, reagents and materials used in the present invention are commercially available.

Example 1

[0029] Molar percentages of chemical constituents of a glass in the present example are as follows: 30B.sub.2O.sub.3-40SiO.sub.2-5ZnO-7Al.sub.2O.sub.3-6Cs.sub.2CO.sub.3-4(Pb/Mn)Cl.sub.2-4NaCl-4MCO.sub.3, wherein M is Sr.

TABLE-US-00001 TABLE 1 Material constituents of a divalent manganese-doped all-inorganic perovskite quantum dot glass of Example 1 Material H.sub.3BO.sub.3 SiO.sub.2 Al.sub.2O.sub.3 Cs.sub.2CO.sub.3 PbCl.sub.2 MnCl.sub.2 NaCl SrCO.sub.3 ZnO Mass 12.9849 8.4118 2.4981 6.8422 1.9468 0.8809 0.8182 2.066 1.1397

[0030] Mass of each compound correspondingly shown in Table 1 can be calculated according to the molar percentages of the chemical constituents of Example 1. Analytically pure H.sub.3BO.sub.3, SiO.sub.2, Al.sub.2O.sub.3, Cs.sub.2CO.sub.3, PbCl.sub.2, MnCl.sub.2, NaCl, SrCO.sub.3 and ZnO were accurately weighed according to Table 1. The materials accurately weighed were ground in an agate mortar for 1 to 2 hours, and transferred to a corundum crucible to be melted at 1200 C. for 30 minutes. Then the melt was poured into a preheated graphite mold for molding, followed by being annealed in an annealing furnace at 360 C. for 4 hours. As the furnace was cooled, an original glass was obtained and denoted as QD-Glass-CsPbCl.sub.3Mn. The original glass was subsequently put in a thermal treatment furnace for thermal treatment respectively at 470 C.-550 C. for 10 to 20 hours. As the furnace was cooled to room temperature, a divalent manganese-doped all-inorganic perovskite quantum dot glass sample was obtained. The glass sample was cut into an appropriate thickness with a diamond linear cutter and polished until both sides became mirror surface, and then a satisfactory divalent manganese-doped all-inorganic perovskite quantum dot glass was achieved. Particularly, FIG. 1 is an XRD diagram of the divalent manganese-doped all-inorganic perovskite quantum dot glass synthesized by thermal treatment at 500 C. for 10 hours. It can be known from the figure that diffraction peaks present in the glass obtained by the thermal treatment respectively correspond to a cubic-phase CsPbCl.sub.3 standard card PDF #75-0411, thereby indicating that the CsPbCl.sub.3 perovskite quantum dots were separated out of the glass.

Example 2

[0031] Molar percentages of chemical constituents of a glass in the present example are as follows: 35B.sub.2O.sub.3-35SiO.sub.2-4ZnO-7Al.sub.2O.sub.3-6Cs.sub.2CO.sub.3-4(Pb/Mn)Cl.sub.2-4NaCl-5MCO.sub.3, wherein M is Ca.

TABLE-US-00002 TABLE 2 Material constituents of a divalent manganese-doped all-inorganic perovskite quantum dot glass of Example 2 Material H.sub.3BO.sub.3 SiO.sub.2 Al.sub.2O.sub.3 Cs.sub.2CO.sub.3 PbCl.sub.2 MnCl.sub.2 NaCl SrCO.sub.3 ZnO Mass 15.1491 7.3603 2.4981 6.8422 1.9468 0.8809 0.8182 1.7515 1.1397

[0032] Mass of each compound correspondingly shown in Table 2 can be calculated according to the molar percentages of the chemical constituents of Example 2. Analytically pure H.sub.3BO.sub.3, SiO.sub.2, Al.sub.2O.sub.3, Cs.sub.2CO.sub.3, PbCl.sub.2, MnCl.sub.2, NaCl, CaCO.sub.3 and ZnO were accurately weighed according to Table 2. The materials accurately weighed were ground in an agate mortar for 1 to 2 hours, and transferred to a corundum crucible to be melted at 1300 C. for 30 minutes. Then the melt was poured into a preheated graphite mold for molding, followed by being annealed in an annealing furnace at 360 C. for 4 hours. As the furnace was cooled, an original glass was obtained and denoted as QD-Glass-CsPbCl.sub.3Mn. The original glass was subsequently put in a thermal treatment furnace for thermal treatment respectively at 470 C.-550 C. for 10 to 20 hours. As the furnace was cooled to room temperature, a divalent manganese-doped all-inorganic perovskite quantum dot glass sample was obtained. The glass sample was cut into an appropriate thickness with a diamond linear cutter and polished until both sides became mirror surface, and then a satisfactory divalent manganese-doped all-inorganic perovskite quantum dot glass was achieved. Particularly, FIG. 2 is a TEM diagram of the divalent manganese-doped all-inorganic perovskite quantum dot glass synthesized by thermal treatment at 515 C. for 15 hours. It can be known from the figure that the CsPbCl.sub.3 perovskite quantum dots separated out of the glass are crystals having a size of 8 nm-15 nm, and it can be seen from the high-resolution TEM that a lattice spacing of the quantum dot glass corresponds to a lattice plane of the CsPbCl.sub.3 quantum dots (111), further indicating that the quantum dots synthesized are all-inorganic perovskite CsPbCl.sub.3 quantum dot glass.

Example 3

[0033] Molar percentages of chemical constituents of a glass in the present example are as follows: 34B.sub.2O.sub.3-38SiO.sub.2-4ZnO-5Al.sub.2O.sub.3-6Cs.sub.2CO.sub.3-4(Pb/Mn)Cl.sub.2-4NaCl5MCO.sub.3, wherein M is Sr.

TABLE-US-00003 TABLE 3 Material constituents of a divalent manganese-doped all-inorganic perovskite quantum dot glass of Example 3 Material H.sub.3BO.sub.3 SiO.sub.2 Al.sub.2O.sub.3 Cs.sub.2CO.sub.3 PbCl.sub.2 MnCl.sub.2 NaCl SrCO.sub.3 ZnO Mass 14.7163 7.9912 1.7843 6.8422 1.7522 0.5285 0.8182 2.5835 1.1397

[0034] Mass of each compound correspondingly shown in Table 3 can be calculated according to the molar percentages of the chemical constituents of Example 3. Analytically pure H.sub.3BO.sub.3, SiO.sub.2, Al.sub.2O.sub.3, Cs.sub.2CO.sub.3, PbCl.sub.2, MnCl.sub.2, NaCl, SrCO.sub.3 and ZnO were accurately weighed according to Table 3. The materials accurately weighed were ground in an agate mortar for 1 to 2 hours, and transferred to a corundum crucible to be melted at 1250 C. for 30 minutes. Then the melt was poured into a preheated graphite mold for molding, followed by being annealed in an annealing furnace at 360 C. for 4 hours. As the furnace was cooled, an original glass was obtained and denoted as QD-Glass-CsPbCl.sub.3Mn. The original glass was subsequently put in a thermal treatment furnace for thermal treatment respectively at 470 C.-550 C. for 10 to 20 hours. As the furnace was cooled to room temperature, a divalent manganese-doped all-inorganic perovskite quantum dot glass sample was obtained. The glass sample was cut into an appropriate thickness with a diamond linear cutter and polished until both sides became mirror surface, and then a satisfactory divalent manganese-doped all-inorganic perovskite quantum dot glass was achieved. Particularly, FIG. 3 is an absorption spectrum of the divalent manganese-doped all-inorganic perovskite quantum dot glass obtained by thermal treatment at 520 C. for 10 hours. It can be known from the figure that absorption spectrum of the glass obtained by thermal treatment are similar to those of the CsPbCl.sub.3 quantum dots synthesized by the liquid phase method in the references, also indicating that the quantum dots separated out of the glass were CsPbCl.sub.3 quantum dots.

Example 4

[0035] Molar percentages of chemical constituents of a glass in the present example are as follows: 32B.sub.2O.sub.3-38SiO.sub.2-3ZnO7Al.sub.2O.sub.3-8Cs.sub.2CO.sub.3-3(Pb/Mn)Cl.sub.2-3NaCl6MCO.sub.3, wherein M is Ba.

TABLE-US-00004 TABLE 4 Material constituents of a divalent manganese-doped all-inorganic perovskite quantum dot glass of Example 4 Material H.sub.3BO.sub.3 SiO.sub.2 Al.sub.2O.sub.3 Cs.sub.2CO.sub.3 PbCl.sub.2 MnCl.sub.2 NaCl BaCO.sub.3 ZnO Mass 13.8504 7.9912 2.4981 9.1230 2.0442 0.8809 0.3964 4.1441 0.8548

[0036] Mass of each compound correspondingly shown in Table 4 can be calculated according to the molar percentages of the chemical constituents of Example 4. Analytically pure H.sub.3BO.sub.3, SiO.sub.2, Al.sub.2O.sub.3, Cs.sub.2CO.sub.3, PbCl.sub.2, MnCl.sub.2, NaCl, BaCO.sub.3 and ZnO were accurately weighed according to Table 4. The materials accurately weighed were ground in an agate mortar for 1 to 2 hours, and transferred to a corundum crucible to be melted at 1350 C. for 30 minutes. Then the melt was poured into a preheated graphite mold for molding, followed by being annealed in an annealing furnace at 360 C. for 4 hours. As the furnace was cooled, an original glass was obtained and denoted as QD-Glass-CsPbCl.sub.3Mn. The original glass was subsequently put in a thermal treatment furnace for thermal treatment respectively at 470 C.-550 C. for 10 to 20 hours. As the furnace was cooled to room temperature, a divalent manganese-doped all-inorganic perovskite quantum dot glass sample was obtained. The glass sample was cut into an appropriate thickness with a diamond linear cutter and polished until both sides became mirror surface, and then a satisfactory divalent manganese-doped all-inorganic perovskite quantum dot glass was achieved. Particularly, FIG. 4 is an excitation and emission spectrum of the divalent manganese-doped all-inorganic perovskite quantum dot glass obtained by thermal treatment at 530 C. for 10 hours. It can be known from the figure that the excitation and emission spectrum of the glass obtained by thermal treatment is similar to that of the Mn.sup.2+-doped CsPbCl.sub.3 quantum dots synthesized by the liquid phase method in the references, also indicating that the quantum dots separated out of the glass might be Mn.sup.2+-doped CsPbCl.sub.3 quantum dot glass. The Mn.sup.2+-doped CsPbCl.sub.3 quantum dots in the glass synthesized in the present invention have relatively good chemical stability due to the glass host. The sample has an emission wavelength covering from 525 nm to 800 nm, peaking at 640 nm with full width at half-maximum of 100 nm, and a photoluminescence quantum yield of 23.6%.

TABLE-US-00005 TABLE 5 Internal quantum yield, absorption rate and external quantum yield of the sample synthesized in Example 4 Sample IQY Abs EQY QD-Glass-CsPbCl.sub.3Mn 0.236 0.894 0.211

Example 5

[0037] Molar percentages of chemical constituents of a glass in the present example are as follows: 34B.sub.2O.sub.3-38SiO.sub.2-6ZnO5Al.sub.2O.sub.3-8Cs.sub.2CO.sub.3-3(Pb/Mn)Cl.sub.2-3NaCl3MCO.sub.3, wherein M is Ba.

TABLE-US-00006 TABLE 6 Material constituents of a divalent manganese-doped all-inorganic perovskite quantum dot glass of Example 5 Material H.sub.3BO.sub.3 SiO.sub.2 Al.sub.2O.sub.3 Cs.sub.2CO.sub.3 PbCl.sub.2 MnCl.sub.2 NaCl BaCO.sub.3 ZnO Mass 14.7163 7.9912 1.7843 6.8422 1.4601 0.6607 0.6136 2.0720 1.7096

[0038] Mass of each compound correspondingly shown in Table 6 can be calculated according to the molar percentages of the chemical constituents of Example 5. Analytically pure H.sub.3BO.sub.3, SiO.sub.2, Al.sub.2O.sub.3, Cs.sub.2CO.sub.3, PbCl.sub.2, MnCl.sub.2, NaCl, BaCO.sub.3 and ZnO were accurately weighed according to Table 6. The materials accurately weighed were ground in an agate mortar for 1 to 2 hours, and transferred to a corundum crucible to be melted at 1400 C. for 30 minutes. Then the melt was poured into a preheated graphite mold for molding, followed by being annealed in an annealing furnace at 360 C. for 4 hours. As the furnace was cooled, an original glass was obtained and denoted as QD-Glass-CsPbCl.sub.3Mn. The original glass was subsequently put in a thermal treatment furnace for thermal treatment respectively at 470 C.-550 C. for 10 to 20 hours. As the furnace was cooled to room temperature, a divalent manganese-doped all-inorganic perovskite quantum dot glass sample was obtained. The glass sample was cut into an appropriate thickness with a diamond linear cutter and polished until both sides became mirror surface, and then a satisfactory divalent manganese-doped all-inorganic perovskite quantum dot glass was achieved. Particularly, FIG. 5 is a lifetime curve of the divalent manganese-doped all-inorganic perovskite quantum dot glass obtained by thermal treatment at 530 C. for 20 hours. It can be known from the figure that the lifetime of the glass obtained by thermal treatment is similar to that of the Mn.sup.2+-doped CsPbCl.sub.3 quantum dots synthesized by the liquid phase method in the references, further indicating that the quantum dots separated out of the glass might be Mn.sup.2+-doped CsPbCl.sub.3 quantum dot glass.

Comparative Example 1

[0039] Molar percentages of chemical constituents of a glass in the present comparative example are as follows: 33B.sub.2O.sub.3-38SiO.sub.2-10ZnO5Al.sub.2O.sub.3-8Cs.sub.2CO.sub.3-3(Pb/Mn)Cl.sub.2-3NaCl.

TABLE-US-00007 TABLE 7 Material constituents of a divalent manganese-doped glass of Comparative Example 1 Material H.sub.3BO.sub.3 SiO.sub.2 Al.sub.2O.sub.3 Cs.sub.2CO.sub.3 PbCl.sub.2 MnCl.sub.2 NaCl ZnO Mass 14.7163 7.9912 1.7843 6.8422 2.3362 0.2643 0.6136 2.8493

[0040] Mass of each compound correspondingly shown in Table 7 can be calculated according to the molar percentages of the chemical constituents of Comparative Example 1. Analytically pure H.sub.3BO.sub.3, SiO.sub.2, Al.sub.2O.sub.3, Cs.sub.2CO.sub.3, PbCl.sub.2, MnCl.sub.2, NaCl and ZnO were accurately weighed according to Table 7. The materials accurately weighed were ground in an agate mortar for 1 to 2 hours, and transferred to a corundum crucible to be melted at 1250 C. for 30 minutes. Then the melt was poured into a preheated graphite mold for molding, followed by being annealed in an annealing furnace at 360 C. for 4 hours. As the furnace was cooled, an original glass was obtained and denoted as Glass-Mn. The original glass was subsequently put in a thermal treatment furnace for thermal treatment respectively at 470 C.-550 C. for 10 to 20 hours. As the furnace was cooled to room temperature, a manganese-doped glass was obtained. The glass was cut into an appropriate thickness with a diamond linear cutter and polished until both sides became mirror surface, and then a manganese-doped glass sample was achieved. Particularly, FIG. 6 is an absorption spectrum of the manganese-doped glass sample obtained by thermal treatment at 520 C. for 15 hours. It can be known from the figure that there's no absorption between 300 nm and 400 nm in the glass obtained by thermal treatment of Comparative Example 1, indicating that a divalent manganese-doped all-inorganic perovskite quantum dot glass cannot be synthesized by the constituents in Comparative Example 1.