A blue-green adjustable light-emitting perovskite quantum dot borosilicate glass material, a preparation method and application thereof

Abstract

The present application relates to the technical field of solid light emitting material, in particular to a kind of blue-green adjustable light emitting perovskite quantum dot borosilicate glass material and its preparation method and application.The present application is by CsPb(Cl / Br)3 perovskite quantum dot is doped into borosilicate glass, not only improve the environmental stability of blue-green adjustable light emitting perovskite quantum dot borosilicate glass material, effectively exert the photoelectric performance of perovskite quantum dot.Moreover, the blue-green adjustable light emitting perovskite quantum dot borosilicate glass material provided by the present application has excellent temperature resilience, when it is heated from room temperature to 280 DEG C and then cooled to room temperature, the luminescent intensity when cooling is comparable to the luminescent intensity in the heating process at the same temperature.

Description

Technical Field

[0001] This invention relates to the field of solid-state luminescent materials technology, specifically to a blue-green tunable luminescent perovskite quantum dot borosilicate glass material, its preparation method, and its applications. Background Technology

[0002] Perovskite quantum dots are semiconductor nanoparticles with a perovskite crystal structure (a cubic crystal structure with the formula ABX3). These nanoparticles exhibit quantum confinement effects, meaning their optical and electrical properties are influenced by their size and shape. Perovskite quantum dot materials possess excellent optoelectronic properties, such as high fluorescence quantum yield, tunable bandgap, and narrow emission bandgap, making them promising for applications in LEDs, laser lighting, and optical sensing. However, traditional perovskite quantum dot materials are susceptible to degradation due to environmental factors (such as humidity, heat, and oxygen), resulting in poor environmental stability in practical applications and severely limiting their application in the optoelectronic field. Summary of the Invention

[0003] In view of this, the purpose of this invention is to provide a blue-green tunable luminescent perovskite quantum dot borosilicate glass material, its preparation method, and its applications. The perovskite quantum dots in the blue-green tunable luminescent perovskite quantum dot borosilicate glass material provided by this invention exhibit good environmental stability.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0005] This invention provides a blue-green tunable luminescent perovskite quantum dot borosilicate glass material, whose chemical composition, by molar percentage, includes: 52-64 parts H3BO3, 26-32 parts SiO2, 4-10 parts ZnO, 10-17 parts Na2CO3, 5-10 parts Cs2CO3, 15-24 parts PbX2, and 6-16 parts NaX, wherein X is Cl and / or Br.

[0006] Preferably, when X is Cl and Br, the molar ratio of PbCl2 to PbBr2 is 0-19:0-19; and the molar ratio of NaCl2 to NaBr2 is 0-11:0-11.

[0007] Preferably, the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material, by molar amount, includes 52-64 parts of H3BO3, 26-32 parts of SiO2, 4-10 parts of ZnO, 10-17 parts of Na2CO3, 8 parts of Cs2CO3, 19 parts of PbX2, and 11 parts of NaX, wherein X is Cl and / or Br.

[0008] This invention provides a method for preparing the blue-green tunable luminescent perovskite quantum dot borosilicate glass material described in the above technical solution, comprising the following steps:

[0009] According to the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material, the raw materials are mixed and melted to obtain a glass melt;

[0010] The glass melt is cast and cooled to obtain the blue-green tunable luminescent perovskite quantum dot borosilicate glass material;

[0011] Preferably, the melting temperature is 1000–1200°C and the melting time is 10–30 min.

[0012] Preferably, the mixing includes grinding and mixing; the particle size of the mixture obtained by grinding and mixing is 1 to 5 μm.

[0013] Preferably, the casting time is <6 minutes.

[0014] Preferably, the casting process includes: pouring the glass melt onto a preheated plate and allowing it to stand.

[0015] Preferably, the temperature of the preheated plate is 300-450°C; and the pouring time is <1 min.

[0016] This invention provides the application of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material described in the above technical solution or the blue-green tunable luminescent perovskite quantum dot borosilicate glass material prepared by the preparation method described in the above technical solution in LEDs, laser lighting or optical sensing.

[0017] This invention provides a blue-green tunable luminescent perovskite quantum dot borosilicate glass material. Its chemical composition, by molar percentage, includes: 52-64 parts H3BO3, 26-32 parts SiO2, 4-10 parts ZnO, 10-17 parts Na2CO3, 5-10 parts Cs2CO3, 15-24 parts PbX2, and 6-16 parts NaX, where X is Cl and / or Br. By doping CsPb(Cl / Br)3 perovskite quantum dots into borosilicate glass, this invention not only improves the environmental stability of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material and effectively utilizes the photoelectric properties of perovskite quantum dots, but also provides excellent temperature resilience. When heated from room temperature to 280°C and then cooled back to room temperature, the luminescence intensity during cooling is comparable to that during the heating process at the same temperature.

[0018] Furthermore, by adjusting the ratio of Cl and Br in the blue-green tunable luminescence perovskite quantum dot borosilicate glass material, this invention obtained a blue-green tunable luminescence perovskite quantum dot borosilicate glass material ranging from 414 to 522 nm.

[0019] The method for preparing blue-green tunable luminescent perovskite quantum dot borosilicate glass material provided by the present invention successfully prepares blue-green tunable luminescent perovskite quantum dot borosilicate glass material in borosilicate glass through a self-crystallization method. The preparation process does not require further annealing and heat treatment, is simple to operate, low in cost, low in energy consumption, and has little environmental pollution, making it suitable for industrial production. Attached Figure Description

[0020] Figure 1 The XRD diffraction patterns of the blue-green tunable luminescent perovskite quantum dot borosilicate glass materials prepared in Examples 1-5 are shown below.

[0021] Figure 2 Transmission electron microscope images of the blue-green tunable luminescent perovskite quantum dot borosilicate glass materials prepared in Examples 1-5;

[0022] Figure 3 This is a particle size distribution diagram of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material prepared in Example 5;

[0023] Figure 4 The emission spectra of the blue-green tunable luminescent perovskite quantum dot borosilicate glass materials prepared in Examples 1-5 are shown below.

[0024] Figure 5 The absorption spectra of the blue-green tunable luminescent perovskite quantum dot borosilicate glass materials prepared in Examples 1-5 are shown below.

[0025] Figure 6 The graph shows the temperature-dependent luminescence intensity variation of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material prepared in Example 5. Detailed Implementation

[0026] This invention provides a blue-green tunable luminescent perovskite quantum dot borosilicate glass material, whose chemical composition, by molar percentage, includes: 52-64 parts H3BO3, 26-32 parts SiO2, 4-10 parts ZnO, 10-17 parts Na2CO3, 5-10 parts Cs2CO3, 15-24 parts PbX2, and 6-16 parts NaX, wherein X is Cl and / or Br.

[0027] The chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material provided by the present invention includes 52 to 64 parts of H3BO3, based on the amount of substance. In specific embodiments, the amount of H3BO3 can be 52, 54, 56, 58, 60, 62, or 64 parts.

[0028] Based on the amount of H3BO3, the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material provided by the present invention includes 26 to 32 parts of SiO2. In specific embodiments, the amount of SiO2 can be 26, 27, 28, 29, 30, 31, or 32 parts.

[0029] Based on the amount of H3BO3, the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material provided by the present invention includes 4 to 10 parts of ZnO. In specific embodiments, the amount of ZnO can be 4, 5, 6, 7, 8, 9, or 10 parts.

[0030] Based on the amount of H3BO3, the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material provided by the present invention includes 10 to 17 parts of Na2CO3. In specific embodiments, the amount of Na2CO3 can be 10, 11, 12, 13, 14, 15, 16, or 17 parts.

[0031] Based on the amount of H3BO3, the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material provided by the present invention includes 5 to 10 parts of Cs2CO3. In specific embodiments, the amount of Cs2CO3 can be 5, 6, 7, 8, 9, or 10 parts.

[0032] Based on the amount of H3BO3, the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material provided by the present invention includes 15 to 24 parts of PbX2. In specific embodiments, the amount of PbBr2 can be 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24 parts. In this invention, when X is Cl and Br, the molar ratio of PbCl2 and PbBr2 can be 0 to 19:0 to 19. In specific embodiments, the molar ratio of PbCl2 and PbBr2 can be 0:19, 1:18, 2:17, 3:16, 4:15, 5:14, 6.33:12.67, 7:12, 8:11, 9:10, 9.5:9.5, 11:8, 12:7, 12.67:6.33, 15:4, 17:2, or 19:0.

[0033] Based on the molar amount of H3BO3, the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material provided by this invention includes 6-16 parts of NaX. In specific embodiments, the molar amount of PbI2 can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 parts. In this invention, when X is Cl and Br, the molar ratio of NaCl2 to NaBr2 can be 0-11:0-11. In specific embodiments, the molar ratio of NaCl2 to NaBr2 can be 0:11, 1:10, 2:9, 3.67:7.33, 5.5:5.5, 7.33:3.67, 9:2, 10:1, or 11:0.

[0034] In this invention, the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material may include 52-64 parts of H3BO3, 26-32 parts of SiO2, 4-10 parts of ZnO, 10-17 parts of Na2CO3, 8 parts of Cs2CO3, 19 parts of PbX2, and 11 parts of NaX, by weight.

[0035] This invention provides a method for preparing the blue-green tunable luminescent perovskite quantum dot borosilicate glass material described in the above technical solution, comprising the following steps:

[0036] According to the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material, the raw materials are mixed and melted to obtain a glass melt;

[0037] The glass melt is cast and then cooled to obtain the blue-green tunable luminescent perovskite quantum dot borosilicate glass material.

[0038] Unless otherwise specified, the materials and equipment used in this invention are all commercially available products in the field.

[0039] According to the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material, the present invention involves mixing and melting the raw materials to obtain a glass melt. In specific embodiments, the types and amounts of the raw materials can be the same as those of the chemical composition of the prepared blue-green tunable luminescent perovskite quantum dot borosilicate glass material, and will not be elaborated further here.

[0040] In this invention, the melting temperature can be 1000–1200°C. In specific embodiments, the melting temperature can be 1000°C, 1050°C, 1100°C, 1150°C, or 1200°C. The melting time can be 10–30 min. In specific embodiments, the melting time can be 10 min, 15 min, 20 min, 25 min, or 30 min. In specific embodiments, the mixing can include grinding and mixing. This invention does not have specific limitations on the grinding and mixing time or the particle size of the mixture obtained by grinding and mixing, as long as the raw materials are completely mixed. In specific embodiments, the particle size of the mixture obtained by grinding and mixing can be 1–5 μm, specifically 1 μm, 2 μm, 3 μm, 4 μm, or 5 μm.

[0041] The present invention can place the mixture obtained by mixing in a crucible, and then place the crucible in a muffle furnace for melting. In a specific embodiment, the crucible can be an alumina crucible; the muffle furnace can be a silicon carbide muffle furnace.

[0042] After obtaining the glass melt, the present invention casts and cools the glass melt to obtain the blue-green tunable luminescent perovskite quantum dot borosilicate glass material.

[0043] In this invention, the casting time can be <6 min. In specific embodiments, the casting time can be 5.2 min, 5.3 min, 5.4 min, 5.5 min, 5.6 min, 5.7 min, or 5.8 min.

[0044] In this invention, the casting process may include: pouring the molten glass onto a preheated plate and allowing it to stand. In this invention, the temperature of the preheated plate can be 300–450°C. In specific embodiments, the temperature of the preheated plate can be 300°C, 320°C, 350°C, 370°C, 400°C, or 450°C; the pouring time can be <1 minute. This invention, by rapidly (<1 minute) pouring the molten glass onto the preheated plate, prevents the molten glass from cooling and solidifying due to excessively slow pouring speed, making it impossible to pour out.

[0045] In this invention, the settling temperature can be the same as the temperature of the preheated plate, which will not be elaborated further here. This invention allows the preheated plate to stand after casting to prevent a rapid drop in the temperature of the molten glass from causing the glass block to shatter.

[0046] In this invention, the cooling may include natural cooling; the final cooling temperature may be room temperature. This invention utilizes a self-crystallization method, eliminating the need for further annealing and heat treatment, simplifying operation and reducing energy consumption in the preparation process.

[0047] This invention provides the application of the blue-green tunable light-emitting perovskite quantum dot borosilicate glass material described in the above-described technical solution, or the blue-green tunable light-emitting perovskite quantum dot borosilicate glass material prepared by the above-described technical solution, in displays, lighting, or optical communications. The blue-green tunable light-emitting perovskite quantum dot borosilicate glass material provided by this invention exhibits good environmental stability and excellent temperature resilience, and its blue-green luminescence is tunable from 414nm to 522nm. When applied to LEDs, laser lighting, or optical sensing, its photoelectric properties remain stable in harsh environments.

[0048] To further illustrate the present invention, the following detailed description, in conjunction with embodiments, of a blue-green tunable luminescent perovskite quantum dot borosilicate glass material, its preparation method, and its applications, is provided by the present invention, but these descriptions should not be construed as limiting the scope of protection of the present invention.

[0049] Example 1

[0050] The raw materials for preparation, including 58 parts of H3BO3, 29 parts of SiO2, 7 parts of ZnO, 15 parts of Na2CO3, 8 parts of Cs2CO3, 19 parts of PbCl2 and 11 parts of NaCl, were ground and mixed to a particle size of 2 μm. The mixture was then placed in an alumina crucible, covered and placed in a muffle furnace. The mixture was melted at 1100℃ for 15 min to obtain a glass melt.

[0051] The obtained glass melt was poured into a preheated plate preheated to 400°C within 1 minute, left to stand for 5 minutes, and then allowed to cool naturally to room temperature to obtain a blue-green tunable luminescent perovskite quantum dot borosilicate glass material (denoted as PG1).

[0052] Example 2

[0053] Blue-green tunable luminescent perovskite quantum dot borosilicate glass material (denoted as PG2) was prepared according to the preparation method in Example 1. The only difference from Example 1 is that, in terms of molar amounts, the raw materials used in the preparation are: 58 parts H3BO3, 29 parts SiO2, 7 parts ZnO, 15 parts Na2CO3, 8 parts Cs2CO3, 7 parts PbBr2, 12 parts PbCl2, 2 parts NaBr, and 11 parts NaCl.

[0054] Example 3

[0055] Blue-green tunable luminescent perovskite quantum dot borosilicate glass material (denoted as PG3) was prepared according to the preparation method in Example 1. The only difference from Example 1 is that, in terms of molar amounts, the raw materials used in the preparation are: 58 parts H3BO3, 29 parts SiO2, 7 parts ZnO, 15 parts Na2CO3, 8 parts Cs2CO3, 9.5 parts PbBr2, 9.5 parts PbCl2, 5.5 parts NaBr, and 5.5 parts NaCl.

[0056] Example 4

[0057] Blue-green tunable luminescent perovskite quantum dot borosilicate glass material (denoted as PG4) was prepared according to the preparation method in Example 1. The only difference from Example 1 is that, in terms of molar amounts, the raw materials used in the preparation are: 58 parts H3BO3, 29 parts SiO2, 7 parts ZnO, 15 parts Na2CO3, 8 parts Cs2CO3, 12 parts PbBr2, 7 parts PbCl2, 9 parts NaBr, and 2 parts NaCl.

[0058] Example 5

[0059] Blue-green tunable luminescent perovskite quantum dot borosilicate glass material (denoted as PG5) was prepared according to the preparation method in Example 1. The only difference from Example 1 is that, in terms of molar amounts, the raw materials used in the preparation are: 58 parts H3BO3, 29 parts SiO2, 7 parts ZnO, 15 parts Na2CO3, 8 parts Cs2CO3, 19 parts PbBr2, and 11 parts NaBr.

[0060] Figure 1 The images show the XRD diffraction patterns of the blue-green tunable luminescent perovskite quantum dot borosilicate glass materials prepared in Examples 1-5. Figure 1 It can be seen that the blue-green tunable luminescent perovskite quantum dot borosilicate glass materials prepared in Examples 1-5 all have XRD diffraction peaks corresponding to CsPbCl3 perovskite quantum dots, and their PDF card number is 75-0408 (the CsPbBr3 standard PDF card and the CsPbCl3 standard PDF card only differ in the position of the diffraction peaks, therefore CsPb(Cl / Br)3, CsPbBr3, and CsPbCl3 can all correspond to the CsPbCl3 standard PDF card, so only the CsPbCl3 standard PDF card was compared). As the Br element content in the glass material increases, the diffraction peaks gradually shift to smaller angles. This is because the radius of Br atoms is larger than that of Cl atoms. Increasing the Br element increases the size of CsPb(Cl / Br)3 perovskite quantum dots, so the XRD diffraction peaks shift to smaller angles.

[0061] Figure 2 This is a transmission electron microscope image of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material prepared in Example 5. Figure 3 This is a particle size distribution diagram of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material prepared in Example 5. Figure 2 and Figure 3 As can be seen from the transmission electron microscope image of PG5, many spherical particles can be observed. These spherical particles are CsPb(Cl / Br)3 perovskite quantum dots with an average diameter of about 3.3 nm.

[0062] Figure 4 The images show the emission spectra of the blue-green tunable luminescent perovskite quantum dot borosilicate glass materials prepared in Examples 1-5. Figure 4 It is known that by adjusting the ratio of Cl and Br in the blue-green tunable luminescence perovskite quantum dot borosilicate glass material, the glass material can achieve blue-green tunable luminescence from 414nm to 522nm.

[0063] Figure 5 The images show the absorption spectra of the blue-green tunable luminescent perovskite quantum dot borosilicate glass materials prepared in Examples 1-5. Figure 5 It can be seen that the absorption spectra of the blue-green tunable luminescent perovskite quantum dot borosilicate glass materials prepared in Examples 1 to 5 also have the characteristic of being blue-green tunable.

[0064] Figure 6 This is a graph showing the temperature-dependent luminescence intensity variation of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material prepared in Example 6. Figure 5 It can be seen that the luminescence intensity of PG5 gradually decreases because the probability of nonradiative transitions increases with increasing temperature, thus reducing the luminescence intensity. However, as the temperature gradually decreases from high temperature to room temperature, the luminescence intensity of the PG5 sample almost recovers to its original value, indicating that the PG5 sample has excellent temperature resilience.

[0065] Comparative Example 1

[0066] Traditional colloidal perovskite quantum dots were prepared according to the literature (Daqin Chen, Shuo Yuan, Jiangkun Chen, et al. Robust CsPbX3 (X=Cl,Br, and I) perovskite quantum dot embedded glasses: nanocrystallization, improved stability and visible full-spectral tunable. [J] Journal of Materials Chemistry C, 2018, 6, 12864).

[0067] Tests showed that the blue-green tunable luminescent perovskite quantum dot borosilicate glass materials provided in Examples 1-5 maintained about 30% of their original luminescence intensity when heated to over 100°C, demonstrating good thermal stability. In contrast, the colloidal perovskite quantum dots prepared in Comparative Example 1 showed only about 8% of their original luminescence intensity when heated to 100°C, indicating poor thermal stability.

[0068] In summary, the blue-green tunable luminescent perovskite quantum dot borosilicate glass material provided by this invention has excellent environmental stability. Moreover, by changing the ratio of Cl and Br in the borosilicate glass and the self-crystallization, CsPb(Cl / Br)3 perovskite quantum dots with tunable blue-green luminescence and good temperature resilience can be prepared in borosilicate glass.

[0069] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A blue-green tunable luminescent perovskite quantum dot borosilicate glass material, wherein the chemical composition, by molar fraction, comprises: H3BO3 52~64 parts, SiO2 26~32 parts, ZnO 4~10 parts, Na2CO3 10~17 parts, Cs2CO3 8 parts, PbX2 19 parts and NaX 11 parts, wherein X is Cl and / or Br; The preparation method of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material comprises the following steps: according to the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material, the raw materials are mixed and melted to obtain a glass melt; the glass melt is cast and cooled to obtain the blue-green tunable luminescent perovskite quantum dot borosilicate glass material.

2. The method for preparing the blue-green tunable luminescent perovskite quantum dot borosilicate glass material according to claim 1, characterized in that, The steps are as follows: according to the chemical composition of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material, the raw materials are mixed and melted to obtain a glass melt; the glass melt is cast and cooled to obtain the blue-green tunable luminescent perovskite quantum dot borosilicate glass material.

3. The preparation method according to claim 2, characterized in that, The melting temperature is 1000~1200℃, and the time is 10~30min.

4. The preparation method according to claim 2, characterized in that, The mixing includes grinding and mixing; the particle size of the mixture obtained by grinding and mixing is 1~5μm.

5. The preparation method according to claim 2, characterized in that, The casting time is less than 6 minutes.

6. The preparation method according to claim 2 or 5, characterized in that, The casting process includes: pouring the glass melt onto a preheated plate and allowing it to stand.

7. The preparation method according to claim 6, characterized in that, The temperature of the preheated plate is 300~450℃; the pouring time is <1min.

8. The application of the blue-green tunable luminescent perovskite quantum dot borosilicate glass material according to claim 1 or the blue-green tunable luminescent perovskite quantum dot borosilicate glass material prepared by any one of claims 2 to 7 in LED, laser lighting or optical sensing.

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