A red light emitting borosilicate perovskite quantum dot glass and a preparation method thereof

Abstract

This invention provides a red-emitting borosilicate perovskite quantum dot glass and its preparation method, belonging to the field of solid-state luminescent materials. This invention obtains red-emitting borosilicate perovskite quantum dot glass through a self-crystallization method. The preparation process does not require annealing or heat treatment, is simple and energy-efficient, and can be mass-produced. Furthermore, the prepared red-emitting borosilicate perovskite quantum dot glass exhibits excellent temperature resilience. The results of the examples demonstrate that the red-emitting borosilicate perovskite quantum dot glass prepared by the method provided in this invention possesses excellent temperature resilience.

Description

Technical Field

[0001] This invention relates to the field of solid-state luminescent materials, and more particularly to a red-emitting borosilicate perovskite quantum dot glass and its preparation method. Background Technology

[0002] In recent years, all-inorganic perovskite quantum dots have attracted widespread attention due to their excellent optical properties, such as high photoluminescence quantum yield, tunable luminescence across the entire visible light spectrum, and high emission color purity. This makes them a strong candidate material for fabricating devices such as LEDs, liquid crystal displays, temperature sensors, and backlight displays. Traditional perovskite quantum dots are typically synthesized using chemical methods, but their ionic crystal properties and low formation energy make it difficult to guarantee long-term stability, severely hindering their practical application in optoelectronics. Oxide glass materials, due to their high stability and ease of fabrication, offer an effective means of improving the stability of perovskite quantum dots by encapsulating them within inorganic glass materials.

[0003] Previously, most research focused on green-emitting CsPbBr3 perovskite quantum dot glasses, while research progress on red-emitting perovskite quantum dot glasses was relatively limited. Furthermore, the preparation of CsPbBr3 perovskite quantum dot glasses often requires annealing and heat treatment, which not only increases energy consumption and costs but also results in a long process, slow production efficiency, and is detrimental to environmental protection.

[0004] Therefore, how to prepare red-emitting borosilicate perovskite quantum dot glass without annealing and heat treatment has become a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] The purpose of this invention is to provide a red light emitting borosilicate perovskite quantum dot glass and its preparation method. The preparation method provided by this invention does not require annealing and heat treatment, and can make the borosilicate perovskite quantum dot glass have excellent temperature resilience.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a method for preparing red-light-emitting borosilicate perovskite quantum dot glass, comprising the following steps:

[0008] (1) H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbX2 and NaX are mixed and melted, and then naturally cooled to obtain perovskite quantum dot glass;

[0009] (2) The perovskite quantum dot glass obtained in step (1) is ball-milled to obtain red light emitting borosilicate perovskite quantum dot glass.

[0010] Preferably, in step (1), the molar ratio of H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbX2 and NaX is (24-49):(9-34):(5-9):(13-17):8:19:11.

[0011] Preferably, the molar ratio of H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbX2 and NaX is 39:19:7:15:8:19:11.

[0012] Preferably, in step (1), PbX2 is PbBr2 and / or PbI2.

[0013] Preferably, the PbX2 is PbBr2 and PbI2, and the molar ratio of PbBr2 to PbI2 is (6-8):(11-13).

[0014] Preferably, in step (1), NaX is NaBr and / or NaI.

[0015] Preferably, the NaX is NaBr and NaI, and the molar ratio of NaBr to NaI is (1-3):(8-10).

[0016] Preferably, in step (2), the ball milling speed is 80-120 rpm and the ball milling time is 1.5-3 hours.

[0017] Preferably, the ball mill rotates at 100 rpm and the milling time is 2 to 2.5 hours.

[0018] This invention provides a red-emitting borosilicate perovskite quantum dot glass prepared by the preparation method described in the above technical solution.

[0019] This invention provides a method for preparing red-emitting borosilicate perovskite quantum dot glass, comprising the following steps: (1) mixing H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbX2, and NaX and melting the mixture, followed by natural cooling to obtain perovskite quantum dot glass; (2) ball milling the perovskite quantum dot glass obtained in step (1) to obtain red-emitting borosilicate perovskite quantum dot glass. This invention obtains red-emitting borosilicate perovskite quantum dot glass through a self-crystallization method. The preparation process does not require annealing or heat treatment, is simple and energy-efficient, and can be mass-produced. Furthermore, the prepared red-emitting borosilicate perovskite quantum dot glass exhibits excellent temperature resilience. The results of the embodiments show that the red-emitting borosilicate perovskite quantum dot glass provided by this invention has excellent temperature resilience. Attached Figure Description

[0020] Figure 1 XRD patterns of red-emitting borosilicate perovskite quantum dot glasses obtained in Examples 1-5;

[0021] Figure 2 This is a TEM image of the red-emitting borosilicate perovskite quantum dot glass obtained in Example 3;

[0022] Figure 3 The image shows the HTEM image of the red-emitting borosilicate perovskite quantum dot glass obtained in Example 3.

[0023] Figure 4 The emission spectra of the red-emitting borosilicate perovskite quantum dot glasses obtained in Examples 1-5 are shown.

[0024] Figure 5 Here is a SEM image of the red-emitting borosilicate perovskite quantum dot glass obtained in Example 2;

[0025] Figure 6 This is a magnified SEM image of the red-emitting borosilicate perovskite quantum dot glass obtained in Example 2;

[0026] Figure 7 The heating spectrum of the red-emitting borosilicate perovskite quantum dot glass obtained in Example 3;

[0027] Figure 8 The cooling spectrum of the red-emitting borosilicate perovskite quantum dot glass obtained in Example 3;

[0028] Figure 9 The curves showing the change in luminescence intensity of the red-emitting borosilicate perovskite quantum dot glass obtained in Example 3 during heating and cooling processes are shown. Detailed Implementation

[0029] This invention provides a method for preparing red-light-emitting borosilicate perovskite quantum dot glass, comprising the following steps:

[0030] (1) H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbX2 and NaX are mixed and melted, and then naturally cooled to obtain perovskite quantum dot glass;

[0031] (2) The perovskite quantum dot glass obtained in step (1) is ball-milled to obtain red light emitting borosilicate perovskite quantum dot glass.

[0032] This invention involves mixing H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbX2, and NaX, melting the mixture, and then naturally cooling it to obtain perovskite quantum dot glass.

[0033] In this invention, unless otherwise specified, all raw materials used are commercially available products known to those skilled in the art or products prepared using processes known to those skilled in the art.

[0034] In this invention, the PbX2 is preferably PbBr2 and / or PbI2, more preferably PbBr2 and PbI2. In this invention, when the PbX2 is PbBr2 and PbI2, the molar ratio of PbBr2 to PbI2 is preferably (6-8):(11-13), more preferably 7:12.

[0035] In this invention, the NaX is preferably NaBr and / or NaI, more preferably NaBr and NaI. In this invention, when the NaX is NaBr and NaI, the molar ratio of NaBr to NaI is preferably (1-3):(8-10), more preferably 2:9.

[0036] In this invention, the preferred molar ratio of H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbX2, and NaX is (24–49):(9–34):(5–9):(13–17):8:19:11, more preferably (34–44):(14–24):7:15:8:19:11, and even more preferably 39:19:7:15:8:19:11. By controlling the ratio of raw materials, this invention can further improve the temperature resilience of glass.

[0037] The present invention does not impose any special limitations on the specific operation of the mixing, which can be determined based on the technical common sense of those skilled in the art.

[0038] In this invention, the melting is preferably carried out in a muffle furnace. This invention does not impose any specific limitations on the model of the muffle furnace; any commercially available muffle furnace well-known to those skilled in the art can be used.

[0039] In this invention, the preferred melting temperature is 1050–1150°C, more preferably 1100°C; the preferred melting time is 5–40 min, more preferably 10–20 min. By controlling the melting process parameters, this invention ensures complete melting of the raw materials, forming a uniform glass melt.

[0040] After melting, the molten glass is preferably poured into a brass mold and then allowed to cool naturally. This natural cooling method avoids a rapid drop in temperature that could lead to a significant increase in internal stress.

[0041] After obtaining the perovskite quantum dot glass, the present invention ball-mills the perovskite quantum dot glass to obtain red light emitting borosilicate perovskite quantum dot glass.

[0042] In this invention, the ball milling is preferably carried out in a ball mill. This invention does not specify a particular model of ball mill; any ball mill well-known to those skilled in the art can be used.

[0043] In this invention, the ball milling speed is preferably 80-120 rpm, more preferably 100 rpm; the ball milling time is preferably 1.5-3 hours, more preferably 2-2.5 hours. This invention improves the luminescence uniformity of red-light-emitting borosilicate perovskite quantum dot glass by ball milling, thereby enhancing the optical performance of the glass.

[0044] In this invention, the particle size of the red-emitting borosilicate perovskite quantum dot glass is preferably 1–5 μm. By controlling the particle size of the glass, this invention can further improve its luminescence uniformity.

[0045] This invention obtains red-emitting borosilicate perovskite quantum dot glass through a self-crystallization method. The preparation process does not require annealing or heat treatment, is simple and energy-saving, and can be mass-produced. Furthermore, the prepared red-emitting borosilicate perovskite quantum dot glass exhibits excellent temperature resilience.

[0046] This invention provides a red-emitting borosilicate perovskite quantum dot glass prepared by the method described above. The red-emitting borosilicate perovskite quantum dot glass prepared by this invention exhibits excellent temperature resilience.

[0047] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0048] Example 1

[0049] A method for preparing red light-emitting borosilicate perovskite quantum dot glass comprises the following steps:

[0050] (1) H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbBr2, PbI2, NaBr and NaI are mixed and melted in a muffle furnace, then poured into a brass mold and naturally cooled to room temperature to obtain perovskite quantum dot glass; the molar ratio of H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbBr2, PbI2, NaI and NaBr is 24:34:7:15:8:7:12:2:9; the melting holding temperature is 1100℃ and the melting holding time is 10min;

[0051] (2) The perovskite quantum dot glass obtained in step (1) is ball-milled in a ball mill to obtain red light emitting borosilicate perovskite quantum dot glass with a particle size of 1-5 μm, denoted as PG1; the ball milling speed is 100 rpm and the ball milling time is 2 h.

[0052] Example 2

[0053] A method for preparing red light-emitting borosilicate perovskite quantum dot glass comprises the following steps:

[0054] (1) H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbBr2, PbI2, NaBr and NaI are mixed and melted in a muffle furnace, then poured into a brass mold and naturally cooled to room temperature to obtain perovskite quantum dot glass; the molar ratio of H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbBr2, PbI2, NaI and NaBr is 34:24:7:15:8:7:12:2:9; the melting holding temperature is 1100℃ and the melting holding time is 10min;

[0055] (2) The perovskite quantum dot glass obtained in step (1) is ball-milled in a ball mill to obtain red light emitting borosilicate perovskite quantum dot glass with a particle size of 1-5 μm, denoted as PG2; the ball milling speed is 100 rpm and the ball milling time is 2 h.

[0056] Example 3

[0057] A method for preparing red light-emitting borosilicate perovskite quantum dot glass comprises the following steps:

[0058] (1) H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbBr2, PbI2, NaBr and NaI are mixed and melted in a muffle furnace, then poured into a brass mold and naturally cooled to room temperature to obtain perovskite quantum dot glass; the molar ratio of H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbBr2, PbI2, NaI and NaBr is 39:19:7:15:8:7:12:2:9; the melting holding temperature is 1100℃ and the melting holding time is 10min;

[0059] (2) The perovskite quantum dot glass obtained in step (1) is ball-milled in a ball mill to obtain red light emitting borosilicate perovskite quantum dot glass with a particle size of 1-5 μm, denoted as PG3; the ball milling speed is 100 rpm and the ball milling time is 2 h.

[0060] Example 4

[0061] A method for preparing red-light-emitting borosilicate perovskite quantum dot glass comprises the following steps:

[0062] (1) H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbBr2, PbI2, NaBr and NaI are mixed and melted in a muffle furnace, then poured into a brass mold and naturally cooled to room temperature to obtain perovskite quantum dot glass; the molar ratio of H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbBr2, PbI2, NaI and NaBr is 44:14:7:15:8:7:12:2:9; the melting holding temperature is 1100℃ and the melting holding time is 10min;

[0063] (2) The perovskite quantum dot glass obtained in step (1) is ball-milled in a ball mill to obtain red light emitting borosilicate perovskite quantum dot glass with a particle size of 1-5 μm, denoted as PG4; the ball milling speed is 100 rpm and the ball milling time is 2 h.

[0064] Example 5

[0065] A method for preparing red-light-emitting borosilicate perovskite quantum dot glass comprises the following steps:

[0066] (1) H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbBr2, PbI2, NaBr and NaI are mixed and melted in a muffle furnace, then poured into a brass mold and naturally cooled to room temperature to obtain perovskite quantum dot glass; the molar ratio of H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbBr2, PbI2, NaI and NaBr is 49:9:7:15:8:7:12:2:9; the melting holding temperature is 1100℃ and the melting holding time is 10min;

[0067] (2) The perovskite quantum dot glass obtained in step (1) is ball-milled in a ball mill to obtain red light emitting borosilicate perovskite quantum dot glass with a particle size of 1-5 μm, denoted as PG5; the ball milling speed is 100 rpm and the ball milling time is 2 h.

[0068] The red-emitting borosilicate perovskite quantum dot glasses obtained in Examples 1-5 were characterized by X-ray diffraction (XRD) (D2 phase shifter, Bruker, Karlsruhe), and the results are as follows: Figure 1 As shown. By Figure 1 It can be seen that perovskite quantum dots have precipitated in the glass.

[0069] The red-emitting borosilicate perovskite quantum dot glass obtained in Example 3 was observed using a JEOL JEM-F200 transmission electron microscope (TEM). The TEM images are shown below. Figure 2 As shown, the obtained HTEM image is as follows: Figure 3 As shown. By Figures 2-3 It can be seen that many spherical particles are precipitated in the glass. The interplanar spacing of these particles is 0.29 nm, which corresponds to the (200) crystal plane of the CsPbBrI2 perovskite quantum dots. This further proves that CsPbBrI2 perovskite quantum dots were successfully prepared in borosilicate glass by self-crystallization method.

[0070] Figure 4 The emission spectra of the red-emitting borosilicate perovskite quantum dot glasses obtained in Examples 1-5 are shown. Figure 4 It can be seen that the emission spectrum peak is located at 637-651 nm, and the glass is brown under sunlight and emits bright red light under ultraviolet light.

[0071] The red-emitting borosilicate perovskite quantum dot glass obtained in Example 2 was observed using a scanning electron microscope. The results obtained at different magnifications are as follows: Figure 5 and Figure 6 As shown. By Figures 5-6 It can be seen that many pores are formed on the glass surface, and the large pores contain white substances. Analysis shows that the phase separation of borosilicate glass causes the pores on the glass surface. The white substances inside the pores are "nano-glass regions", which are a mixture of perovskite quantum dots and glass. Perovskite quantum dots will precipitate from this substance. Phase separation is the reason for the self-crystallization of perovskite quantum dots.

[0072] Figure 7 The temperature rise spectrum of the red-emitting borosilicate perovskite quantum dot glass obtained in Example 3 is shown below. Figure 8 The cooling spectrum of the red-emitting borosilicate perovskite quantum dot glass obtained in Example 3 is shown below. Figure 9 The image shows the luminescence intensity change curve of the red-emitting borosilicate perovskite quantum dot glass obtained in Example 3 during heating and cooling processes. Figures 7-9 It can be seen that as the temperature gradually increases from room temperature, the luminescence intensity of the CsPbBrI2 perovskite quantum dot glass gradually decreases, while as the temperature gradually decreases back to room temperature, the luminescence intensity of the perovskite quantum dot glass gradually increases, and is even higher at the same temperature than when the temperature is increased. This indicates that the borosilicate perovskite quantum dot glass obtained by this invention has excellent temperature resilience.

[0073] 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 method for preparing red-light-emitting borosilicate perovskite quantum dot glass, comprising the following steps: (1) H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbX2 and NaX are mixed and melted, and then naturally cooled to obtain perovskite quantum dot glass; (2) The perovskite quantum dot glass obtained in step (1) is ball-milled to obtain red light emitting borosilicate perovskite quantum dot glass; In step (1), the molar ratio of H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbX2 and NaX is (24~49): (9~34): (5~9): (13~17): 8: 19: 11; In step (1), PbX2 is PbBr2 and PbI2, and the molar ratio of PbBr2 to PbI2 is (6~8):(11~13). The NaX is NaBr and NaI, and the molar ratio of NaBr to NaI is (1~3):(8~10). The red-emitting borosilicate perovskite quantum dot glass has a particle size of 1~5μm.

2. The preparation method according to claim 1, characterized in that, The molar ratio of H3BO3, SiO2, ZnO, Na2CO3, Cs2CO3, PbX2 and NaX is 39:19:7:15:8:19:

11.

3. The preparation method according to claim 1, characterized in that, In step (2), the ball milling speed is 80~120 rpm and the ball milling time is 1.5~3h.

4. The preparation method according to claim 3, characterized in that, The ball mill rotates at 100 rpm for 2 to 2.5 hours.

5. Red-emitting borosilicate perovskite quantum dot glass prepared by any one of the preparation methods described in claims 1 to 4.

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