A red light 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 red light perovskite quantum dot borosilicate glass material and its preparation method and application.The present application improves the photoluminescence fluorescence quantum yield of red light perovskite quantum dot borosilicate glass material by introducing AgI in red light perovskite quantum dot borosilicate glass material.Moreover, the present application improves the water-oxygen stability and thermal stability of red light emitting CsPbBrI2 perovskite quantum dot by embedding perovskite quantum dot in borosilicate glass, and the environmental stability is good, and the optical properties of perovskite quantum dot can also be effectively exerted.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of solid-state luminescent materials, in particular to a red light perovskite quantum dot borosilicate glass material and a preparation method and application thereof. BACKGROUND

[0002] With the rapid development of optoelectronic technology, red luminescent materials have wide application prospects in the fields of display, lighting and optical communication. Among them, perovskite quantum dot materials have attracted widespread attention due to their excellent photoelectric properties (such as high optical absorption coefficient, narrow emission spectral line width, high fluorescence quantum yield and adjustable spectral range). Although encapsulating perovskite quantum dots in glass can improve the stability of perovskite quantum dots, it will also reduce the fluorescence quantum yield, resulting in that the fluorescence quantum yield of the current red light perovskite quantum dot glass is generally low, and it is urgent to design a red light perovskite quantum dot glass with high fluorescence quantum yield. SUMMARY

[0003] Therefore, the purpose of the present application is to provide a red light perovskite quantum dot borosilicate glass material and a preparation method and application thereof. The photoluminescence fluorescence quantum yield of the perovskite quantum dots of the red light perovskite quantum dot borosilicate glass material provided by the present application is high.

[0004] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0005] The present application provides a red light perovskite quantum dot borosilicate glass material, the chemical composition of which comprises, in terms of mass fraction: H3BO3 56-68 parts, SiO2 28-34 parts, ZnO 5-9 parts, Na2CO3 13-17 parts, Cs2CO3 1-5 parts, PbBr2 1-4 parts, PbI2 3-7 parts, NaBr 1-2 parts, NaI 1-4 parts and AgI 0-0.6 parts, and the amount of AgI is not 0.

[0006] Preferably, the chemical composition of the red light perovskite quantum dot borosilicate glass material comprises, in terms of mass fraction: H3BO3 56-68 parts, SiO2 28-34 parts, ZnO 5-9 parts, Na2CO3 13-17 parts, Cs2CO3 3 parts, PbBr2 2 parts, PbI2 5 parts, NaBr 1 part, NaI 3 parts and AgI 0-0.6 parts.

[0007] The present application provides a preparation method of the red light perovskite quantum dot borosilicate glass material described in the above technical solutions, comprising the following steps:

[0008] According to the chemical composition of the red light perovskite quantum dot borosilicate glass material, the preparation raw materials are mixed and melted to obtain a glass melt;

[0009] cooling after casting forming of the glass melt, to obtain the red light perovskite quantum dot borosilicate glass material;

[0010] Preferably, the melting temperature is 1100-1250 DEG C, and the time is 10-20 min.

[0011] Preferably, the mixing comprises grinding mixing; the particle size of the mixed material obtained by the grinding mixing is 2 mu m.

[0012] Preferably, the time of the casting forming is < 6 min.

[0013] Preferably, the casting forming comprises: casting the glass melt onto a preheated preheating plate, and standing.

[0014] Preferably, the temperature of the preheated preheating plate is 400 DEG C.

[0015] Preferably, the time of the casting is < 1 min.

[0016] The application provides the application of the red light perovskite quantum dot borosilicate glass material in display, illumination or optical communication.

[0017] The application provides a red light perovskite quantum dot borosilicate glass material, and the chemical composition comprises, in terms of the amount of substance, H3BO3 56-68 parts, SiO2 28-34 parts, ZnO 5-9 parts, Na2CO3 13-17 parts, Cs2CO3 1-5 parts, PbBr2 1-4 parts, PbI2 3-7 parts, NaBr 1-2 parts, NaI 1-4 parts and AgI 0-0.6 parts, and the amount of AgI is not 0. The application introduces AgI into the red light perovskite quantum dot borosilicate glass material, thereby improving the photoluminescence fluorescence quantum yield of the red light perovskite quantum dot borosilicate glass material. Moreover, the application embeds perovskite quantum dots into borosilicate glass, thereby improving the water-oxygen stability and thermal stability of red light emitting CsPbBrI2 perovskite quantum dots, and the environmental stability is good, and the optical properties of the perovskite quantum dots can be effectively exerted.

[0018] The application provides the preparation method of the red light perovskite quantum dot borosilicate glass material, and the method successfully prepares red light emitting CsPbBrI2 perovskite quantum dots in borate glass through a self-crystallization method, the preparation process does not need further annealing and heat treatment, the operation is simple, the cost is low, the energy consumption is low, the environmental pollution is small, and the method is suitable for industrialized production. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1XRD diffraction pattern of the red perovskite quantum dot borosilicate glass material prepared for Examples 1-4 and Comparative Example 1;

[0020] Figure 2 Emission spectrum of the red perovskite quantum dot borosilicate glass material prepared for Examples 1-4 and Comparative Example 1;

[0021] Figure 3 PLQY plot of the red perovskite quantum dot borosilicate glass material prepared for Comparative Example 1;

[0022] Figure 4 PLQY plot of the red perovskite quantum dot borosilicate glass material prepared for Example 3;

[0023] Figure 5 Lifetime decay curve of the red perovskite quantum dot borosilicate glass material prepared for Examples 1-4 and Comparative Example 1;

[0024] Figure 6 Photoluminescence intensity change plot of the red perovskite quantum dot borosilicate glass material prepared for Example 3 immersed in water for 90 days;

[0025] Figure 7 Photoluminescence intensity change plot of the red perovskite quantum dot borosilicate glass material prepared for Example 3 under continuous irradiation of 6W ultraviolet light for 90 days;

[0026] Figure 8 Photoluminescence intensity change plot of the red perovskite quantum dot borosilicate glass material prepared for Example 3 cycled five times at temperatures of 300K and 400K, respectively. DETAILED DESCRIPTION

[0027] The present application provides a red perovskite quantum dot borosilicate glass material, the chemical composition of which comprises, in terms of mass fraction: H3BO3 56-68 parts, SiO2 28-34 parts, ZnO 5-9 parts, Na2CO3 13-17 parts, Cs2CO3 1-5 parts, PbBr2 1-4 parts, PbI2 3-7 parts, NaBr 1-2 parts, NaI 1-4 parts, and AgI 0-0.6 parts, and the amount of AgI is not 0.

[0028] The red perovskite quantum dot borosilicate glass material provided by the present application has a chemical composition comprising, in terms of mass fraction: H3BO3 56-68 parts, and in specific embodiments, the mass fraction of H3BO3 can be 56 parts, 60 parts, 62 parts, 64 parts, 66 parts, or 68 parts.

[0029] The red light perovskite quantum dot borosilicate glass material provided by the application has a chemical composition including 28-34 parts of SiO2, and in specific embodiments, the amount of SiO2 can be 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts or 34 parts.

[0030] The red light perovskite quantum dot borosilicate glass material provided by the application has a chemical composition including 5-9 parts of ZnO, and in specific embodiments, the amount of ZnO can be 5 parts, 6 parts, 7 parts, 8 parts or 9 parts.

[0031] The red light perovskite quantum dot borosilicate glass material provided by the application has a chemical composition including 13-17 parts of Na2CO3, and in specific embodiments, the amount of Na2CO3 can be 13 parts, 14 parts, 15 parts, 16 parts or 17 parts.

[0032] The red light perovskite quantum dot borosilicate glass material provided by the application has a chemical composition including 1-5 parts of Cs2CO3, and in specific embodiments, the amount of Cs2CO3 can be 1 part, 2 parts, 3 parts, 4 parts or 5 parts.

[0033] The red light perovskite quantum dot borosilicate glass material provided by the application has a chemical composition including 1-4 parts of PbBr2, and in specific embodiments, the amount of PbBr2 can be 1 part, 2 parts, 3 parts or 4 parts.

[0034] The red light perovskite quantum dot borosilicate glass material provided by the application has a chemical composition including 2-7 parts of PbI2, and in specific embodiments, the amount of PbI2 can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts or 7 parts.

[0035] The red light perovskite quantum dot borosilicate glass material provided by the application has a chemical composition including 1-2 parts of NaBr, and in specific embodiments, the amount of NaBr can be 1 part or 2 parts.

[0036] The red light perovskite quantum dot borosilicate glass material provided by the application has a chemical composition including 1-4 parts of NaI, and in specific embodiments, the amount of NaI can be 1 part, 2 parts, 3 parts or 4 parts.

[0037] The red-light perovskite quantum dot borosilicate glass material provided by the present application has a chemical composition including AgI 0-0.6 parts, and the amount of AgI is not 0. In specific embodiments, the amount of AgI can be 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts or 0.6 parts.

[0038] In the present application, the red-light perovskite quantum dot borosilicate glass material has a chemical composition including H3BO356-68 parts, SiO228-34 parts, ZnO 5-9 parts, Na2CO313-17 parts, Cs2CO33 parts, PbBr22 parts, PbI25 parts, NaBr 1 part, NaI 3 parts and AgI 0-0.6 parts.

[0039] The present application provides a preparation method of the red-light perovskite quantum dot borosilicate glass material described in the above technical solution, including the following steps:

[0040] According to the chemical composition of the red-light perovskite quantum dot borosilicate glass material, the preparation raw materials are mixed and melted to obtain a glass melt.

[0041] The glass melt is poured into a mold and cooled to obtain the red-light perovskite quantum dot borosilicate glass material.

[0042] Unless otherwise specified, the materials and equipment used in the present application are commercially available in the art.

[0043] According to the chemical composition of the red-light perovskite quantum dot borosilicate glass material, the preparation raw materials are mixed and melted to obtain a glass melt. In the present application, the types and amounts of the preparation raw materials can be the same as those of the red-light perovskite quantum dot borosilicate glass material prepared, and will not be described here.

[0044] In the present application, the temperature of the melting can be 1100-1250℃, and in specific embodiments, the temperature of the melting can be 1100℃, 1150℃, 1180℃, 1200℃ or 1250℃; the time of the melting can be 10-20min, and in specific embodiments, the time of the melting can be 10min, 12min, 15min, 18min or 20min. In specific embodiments, the mixing can include grinding mixing; the present application does not have special limitations on the time of the grinding mixing and the particle size of the mixed material obtained by the grinding mixing, and the preparation raw materials can be completely mixed. In specific embodiments, the particle size of the mixed material obtained by the grinding mixing can be 1-5μm, and in specific embodiments, the particle size of the mixed material obtained by the grinding mixing can be 1μm, 2μm, 3μm, 4μm or 5μm.

[0045] The present application can place the mixed material obtained by the mixing into a crucible, and place the crucible into a muffle furnace for melting, and in specific embodiments, the crucible can be an alumina crucible; and the muffle furnace can be a silicon carbide muffle furnace.

[0046] After obtaining the glass melt, the present application cools the glass melt after casting forming to obtain the red light perovskite quantum dot borosilicate glass material.

[0047] In the present application, the time of the casting forming can be <6min, and in specific embodiments, the time of the casting forming can be 5.2min, 5.3min, 5.4min, 5.5min, 5.6min, 5.7min or 5.8min.

[0048] In specific embodiments, the casting forming can include: pouring the glass melt onto a preheated preheating plate and standing. In the present application, the temperature of the preheated preheating plate can be 300-450℃, and in specific embodiments, the temperature of the preheated preheating plate can be 300℃, 320℃, 350℃, 370℃, 400℃ or 450℃; and the time of the pouring can be <1min. The present application quickly (<1min) pours the glass melt onto the preheated preheating plate, prevents the glass melt from cooling and solidifying due to too slow pouring speed, and cannot be poured out.

[0049] In specific embodiments, the standing temperature can be the same as the temperature of the preheated preheating plate, which is not described herein again. In specific embodiments, the standing time can be 5min. The present application stands the preheating plate after pouring, prevents the glass melt from rapidly dropping in temperature and causing the glass block to break.

[0050] In specific embodiments, the cooling can comprise natural cooling; the final temperature of the cooling can be room temperature. The present application is simple to operate by the method of self-crystallization without further annealing and heat treatment, and reduces the energy consumption for preparation.

[0051] The present application provides the application of the red light perovskite quantum dot borosilicate glass material in display, lighting or optical communication. The red light perovskite quantum dot borosilicate glass material provided by the present application has high photoluminescence fluorescence quantum yield and good environmental stability, and can maintain stability and high luminous intensity in harsh environments when applied to display, lighting or optical communication.

[0052] In order to further illustrate the present application, the red light perovskite quantum dot borosilicate glass material, the preparation method and the application thereof provided by the present application are described in detail below in combination with examples, but they should not be understood as limiting the protection scope of the present application.

[0053] Example 1

[0054] The preparation raw materials of H3BO364 parts, SiO232 parts, ZnO 7 parts, Na2CO315 parts, Cs2CO33 parts, PbBr22 parts, PbI25 parts, NaBr 1 part, NaI 3 parts and AgI 0.1 part were ground and mixed to a particle size of about 2 μm, loaded into an alumina crucible, covered and placed in a muffle furnace, and melted at 1230℃ for 15 min to obtain a glass melt.

[0055] The obtained glass melt was poured onto a preheated plate preheated to 400℃ within 1 min, placed for 5 min, and then naturally cooled to room temperature to obtain a red light perovskite quantum dot borosilicate glass material (denoted as PG0.1).

[0056] Example 2

[0057] The red light perovskite quantum dot borosilicate glass material (denoted as PG0.2) was prepared according to the preparation method in Example 1, and the only difference from Example 1 was that the preparation raw materials were H3BO364 parts, SiO232 parts, ZnO 7 parts, Na2CO315 parts, Cs2CO33 parts, PbBr22 parts, PbI25 parts, NaBr 1 part, NaI 3 part and AgI 0.2 part in terms of substance amount.

[0058] Example 3

[0059] A red light perovskite quantum dot borosilicate glass material (denoted as PG0.4) was prepared according to the preparation method in Example 1, with the only difference being that the raw materials were H3BO364 parts, SiO232 parts, ZnO 7 parts, Na2CO315 parts, Cs2CO33 parts, PbBr22 parts, PbI25 parts, NaBr 1 part, NaI 3 parts, and AgI 0.4 parts in terms of the amount of substance.

[0060] Example 4

[0061] A red light perovskite quantum dot borosilicate glass material (denoted as PG0.6) was prepared according to the preparation method in Example 1, with the only difference being that the raw materials were H3BO364 parts, SiO232 parts, ZnO 7 parts, Na2CO315 parts, Cs2CO33 parts, PbBr22 parts, PbI25 parts, NaBr 1 part, NaI 3 parts, and AgI 0.6 parts in terms of the amount of substance.

[0062] Comparative Example 1

[0063] A red light perovskite quantum dot borosilicate glass material (denoted as PG) was prepared according to the preparation method in Example 1, with the only difference being that the raw materials were H3BO364 parts, SiO232 parts, ZnO 7 parts, Na2CO315 parts, Cs2CO33 parts, PbBr22 parts, PbI25 parts, NaBr 1 part, and NaI 3 parts in terms of the amount of substance.

[0064] Figure 1 The XRD diffraction patterns of the red light perovskite quantum dot borosilicate glass materials prepared in Examples 1-4 and Comparative Example 1. As can be seen from Figure 1 It can be seen that, without AgI doping (Comparative Example 1), the XRD diffraction peaks exhibit glass steamed bun peaks, and with the increase of the amount of substance of AgI, the XRD diffraction peaks corresponding to the CsPbBrI2 perovskite quantum dots gradually increase, indicating that the doping of AgI is conducive to promoting the precipitation of CsPbBrI2 perovskite quantum dots in the red light perovskite quantum dot borosilicate glass material.

[0065] Figure 2 The emission spectra of the red light perovskite quantum dot borosilicate glass materials prepared in Examples 1-4 and Comparative Example 1. As can be seen from Figure 2It can be seen that the doping of AgI can significantly improve the photoluminescence intensity (PLQY) of the CsPbBrI2 perovskite quantum dots. When the amount-of-substance fraction of AgI is 0.4 parts, the photoluminescence intensity of the CsPbBrI2 perovskite quantum dots reaches the strongest. Further increasing the amount-of-substance fraction of AgI to 0.6 parts reduces the photoluminescence intensity of the CsPbBrI2 perovskite quantum dots, indicating that the doping of AgI can improve the crystallization rate of the CsPbBrI2 perovskite quantum dots in the red perovskite quantum dot borosilicate glass material, and further improve the luminescence intensity of the CsPbBrI2 perovskite quantum dots. However, when the doping concentration of AgI exceeds a certain value, excessive CsPbBrI2 perovskite quantum dots are deposited in the glass, causing concentration quenching phenomenon, resulting in a decrease in the luminescence intensity of the CsPbBrI2 perovskite quantum dot glass. However, compared with the undoped sample PG, the photoluminescence intensity of PG0.6 is still higher.

[0066] Figure 3 The PLQY graph of the red perovskite quantum dot borosilicate glass material prepared for Comparative Example 1. From left to right and top to bottom, the graphs are the photographs of PG under 365 nm ultraviolet light after 0 days, 10 days, 20 days, 30 days, 40 days, 50 days, 60 days, 70 days, 80 days and 90 days, respectively. Figure 3 It can be seen that the PLQY of the red perovskite quantum dot borosilicate glass material prepared for Comparative Example 1 is 20.3%.

[0067] Figure 4 The PLQY graph of the red perovskite quantum dot borosilicate glass material prepared for Example 3. From left to right and top to bottom, the graphs are the photographs of PG under 365 nm ultraviolet light after 0 days, 10 days, 20 days, 30 days, 40 days, 50 days, 60 days, 70 days, 80 days and 90 days, respectively. Figure 4 It can be seen that the red perovskite quantum dot borosilicate glass material prepared for Example 3 is doped with 0.4 parts of AgI in terms of amount-of-substance fraction, and its PLQY is improved to 62.4%.

[0068] Figure 5 The lifetime decay curve graph of the red perovskite quantum dot borosilicate glass materials prepared for Examples 1-4 and Comparative Example 1. From left to right and top to bottom, the graphs are the photographs of PG under 365 nm ultraviolet light after 0 days, 10 days, 20 days, 30 days, 40 days, 50 days, 60 days, 70 days, 80 days and 90 days, respectively. Figure 5 It can be seen that the lifetime values of the red perovskite quantum dot borosilicate glass materials prepared for Comparative Example 1, Example 1, Example 2, Example 3 and Example 4 are 213 ns (nanoseconds), 245 ns, 253 ns, 306 ns and 288 ns, respectively, indicating that the doping of AgI can not only improve the crystallization rate of the CsPbBrI2 perovskite quantum dots in the glass, but also reduce the surface defects of the CsPbBrI2 perovskite quantum dots to a certain extent, and further improve the photoluminescence intensity thereof.

[0069] Figure 6 The photoluminescence intensity change graph of the red perovskite quantum dot borosilicate glass material prepared for Example 3 immersed in water for 90 days, wherein from left to right and top to bottom, the graphs are the photographs of PG0.4 under 365 nm ultraviolet light after 0 days, 10 days, 20 days, 30 days, 40 days, 50 days, 60 days, 70 days, 80 days and 90 days, respectively.Figure 6 It can be seen that after 90 days of immersion in water, PG0.4 still has bright luminescence, and its photoluminescence intensity is 88.9% of the original value, indicating that the prepared red light perovskite quantum dot borosilicate glass material has good water stability.

[0070] Figure 7 This image shows the photoluminescence intensity change of the red-light perovskite quantum dot borosilicate glass material prepared in Example 3 after 90 days of continuous irradiation with 6W ultraviolet light. The inner frame images, from left to right and top to bottom, represent photographs of PG0.4 under a 365nm ultraviolet lamp after 0, 10, 20, 30, 40, 50, 60, 70, 80, and 90 days. Figure 7 It can be seen that after 90 days of ultraviolet light irradiation, PG0.4 still has bright light emission, and its photoluminescence intensity is 90% of the original value, indicating that the prepared red light perovskite quantum dot borosilicate glass material has good photostability.

[0071] Figure 8 The graph shows the photoluminescence intensity changes of the red-light perovskite quantum dot borosilicate glass material prepared in Example 3 after five cycles at 300K and 400K. Figure 8 It can be seen that after 5 cycles of heating and cooling, PG0.4 still has 98% of its original luminescence intensity at room temperature, indicating that the prepared red perovskite quantum dot borosilicate glass material has good thermal stability.

[0072] In summary, this invention enables the preparation of high-luminescence-intensity red perovskite quantum dot borosilicate glass materials in borosilicate glass through AgI doping and self-crystallization. Furthermore, the red perovskite quantum dot borosilicate glass materials provided by this invention exhibit excellent water stability, light stability, and thermal stability, as well as excellent environmental stability.

[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 red light perovskite quantum dot borosilicate glass material, comprising in terms of mole fraction: H3BO3 56-68 parts, SiO2 28-34 parts, ZnO 5-9 parts, Na2CO3 13-17 parts, Cs2CO3 3 parts, PbBr2 2 parts, PbI2 5 parts, NaBr 1 part, NaI 3 parts, and AgI 0-0.6 parts, and the amount of AgI is not 0.

2. The red light calcium perovskite quantum dot borosilicate glass material of claim 1, wherein, The chemical composition of the red light perovskite quantum dot borosilicate glass material includes, in terms of the amount of substance in parts, H3BO3 56-68 parts, SiO2 28-34 parts, ZnO 5-9 parts, Na2CO3 13-17 parts, Cs2CO3 3 parts, PbBr2 2 parts, PbI2 5 parts, NaBr 1 part, NaI 3 parts, and AgI 0-0.6 parts.

3. A method of producing the red light perovskite quantum dot borosilicate glass material according to any one of claims 1 to 2, characterized in that, The method comprises the following steps: According to the chemical composition of the red light perovskite quantum dot borosilicate glass material, the preparation raw materials are mixed and melted to obtain a glass melt. The glass melt is cooled after being cast into shape to obtain the red light perovskite quantum dot borosilicate glass material.

4. The production method according to claim 3, characterized by, The melting temperature is 1100-1250℃, and the time is 10-20 min.

5. The preparation method according to claim 3, characterized in that, The mixing comprises grinding mixing; the particle size of the mixed material obtained by grinding mixing is 1-5 μm.

6. The preparation method according to claim 3, characterized in that, The time of the cast into shape is < 6 min.

7. The production method according to claim 3 or 6, characterized by, The cast into shape comprises: pouring the glass melt onto a preheated preheating plate and standing.

8. The production method according to claim 7, characterized by, The temperature of the preheated preheating plate is 300-450℃.

9. The preparation method according to claim 7, characterized in that, The time of the pouring is < 1 min.

10. The application of the red light perovskite quantum dot borosilicate glass material of any one of claims 1-2 or the red light perovskite quantum dot borosilicate glass material prepared by the preparation method of any one of claims 3-9 in display, lighting or optical communication.

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