A white light emitting phosphate glass material based on divalent tin ions and a method for producing the same

Abstract

The application discloses a white light emitting phosphate glass material based on divalent tin ions and a preparation method thereof, and belongs to the technical field of luminescent glass. The white light emitting phosphate glass material based on divalent tin ions is prepared from raw materials including 2.5-25% of SnO, 15-37.5% of ZnO, 20% of ZnCl2 and 40% of P2O5 in terms of mole percentage; and a reducing agent Si3N4 can be further added when the white light emitting phosphate glass material is prepared. The phosphate glass prepared in air can promote the luminescence of Sn 2+ ; meanwhile, the introduction of the reducing agent can effectively control the valence state of Sn ions, and the phosphate glass has excellent comprehensive performance, a low glass transition temperature, good mechanical performance and thermal stability, and is suitable for white light LED lighting and display devices.

Description

Technical Field

[0001] This invention belongs to the field of light-emitting glass technology, and relates to a white light-emitting phosphate glass material based on divalent tin ions and its preparation method. Background Technology

[0002] To date, white light glass doped with various elements has been increasingly studied in fields such as lighting, communication research, and fiber optic gain. Among various glass matrices, phosphate glass has attracted widespread attention from researchers due to its high transmittance, low phonon energy, low melting temperature, good optical properties, and excellent rare-earth ion solubility characteristics. (The text then abruptly shifts to a different topic: Er...) 3+ Rare earth ions, represented by [specific ion type], have a rich energy level structure and are widely used in optoelectronic materials and devices. However, due to the abundance of their own electronic energy levels and the complexity of their structure, the luminescence bandwidth of a single rare earth ion is limited; co-doping with multiple ions also presents challenges such as the difficulty in controlling the chemical ratio of activating ions to sensitizing ions, thus making it difficult to control luminescence.

[0003] However, in white light glass, by adjusting the glass network structure, one or two transition metal ions can achieve fluorescence coverage in the visible light region, theoretically achieving superior color rendering performance that rare earth ions cannot match. At this point, transition metal ions, with their low cost and rich spectral properties, have attracted attention due to the potential applications of their activated luminescent materials in many fields.

[0004] Among the many transition metal ions, Sn 2+ Sn is gaining increasing attention due to its advantages such as very strong ultraviolet-visible emission, higher richness, and lower price. There is already information about Sn... 2+ Reports of photoluminescence and irradiation in phosphates and borates, and Sn in quartz glass. 2+ The irradiation luminescence intensity of Sn has exceeded that of bismuth germanate (BGO) scintillation crystals. 2+ As a luminescent ion undergoing sp-level transitions, Sn exhibits parity-allowed selection rules, strong luminescence intensity, high quantum efficiency, fluorescence lifetimes reaching several nanoseconds, and a wide emission bandwidth at its luminescent center, making it highly valuable for research. Masai et al. reported on Sn... 2+ -Mn 2 + The photoluminescence properties of co-doped ZnO-P2O5 glass were investigated; the emission color coordinates of this glass under 312 nm excitation were (0.28, 0.33). Zheng Jiajin et al. reported on Sn... 2+ -Dy 3+ Co-doped fluorophosphate glass achieved highly efficient white light emission. When Dy 3+With a doping concentration of 3 wt%, the emission color coordinates under 280 nm excitation are (0.311, 0.330), the quantum efficiency is 56.3%, and the luminance is 6706 cd·m. -2 Yuan Ye and others reported on Sn. 2+ -Mn 2+ Co-doped PSM white light glass was used to obtain a sample with a color rendering index of 91, quantum efficiency of 78%, visible light transmittance of 90%, color coordinates of (0.33, 0.33), and color temperature of 5612 K under excitation at a wavelength of 290 nm. However, current reports focus on Sn... 2+ Sn can be used as a sensitizer and activator in co-doping with other ions to achieve high-efficiency white light emission, but the production cost is high, the energy transfer mechanisms of various ions are complex during the preparation process, and Sn... 4+ Limited research has been conducted on the effect of Sn²⁺ luminescence. Furthermore, the influence of the dosage of reducing agent on luminescence has been almost entirely undiscussed. The luminescence of tin ions in glass primarily originates from the difficult-to-control Sn²⁺. 2+ How to effectively adjust Sn 2+ Improving the luminous intensity by adjusting the ratio of light emission to light intensity remains a bottleneck issue. Summary of the Invention

[0005] The purpose of this invention is to provide a method based on divalent transition metal tin ions (Sn). 2+ This paper describes a method for preparing a white light-emitting phosphate glass material. By combining the adjustment of raw material concentration with the preparation method, a phosphate glass with stable thermodynamic properties, high transmittance, and low transition temperature was prepared. This glass, pumped by a 290nm wavelength laser diode, emitted strong 425nm blue light, making it an ideal material for white LEDs.

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

[0007] A white light emitting phosphate glass material based on divalent tin ions, wherein the raw material composition, by molar percentage, includes: 2.5–25% SnO, 15–37.5% ZnO, 20% ZnCl2 and 40% P2O5.

[0008] Furthermore, the white light emitting phosphate glass material based on divalent tin ions comprises, by molar percentage, 5% SnO, 35% ZnO, 20% ZnCl2 and 40% P2O5.

[0009] Furthermore, the raw materials of the white light emitting phosphate glass material based on divalent tin ions also include a reducing agent, which is Si3N4 powder. The amount of Si3N4 powder added is 0-1.0 wt% of the total mass of SnO, ZnO, ZnCl2, and P2O5 in the raw materials of the white light emitting phosphate glass material based on divalent tin ions, and is not zero. In this invention, the role of the reducing agent is to reduce the oxidation of divalent tin ions to tetravalent tin ions during the firing process, thereby regulating the luminescence performance of the phosphate glass material. The amount of reducing agent added affects the luminescence performance of the phosphate glass material; as the amount of reducing agent added increases, both the excitation intensity and emission intensity of the white light emitting phosphate glass material show a trend of first increasing and then decreasing.

[0010] A method for preparing the white light-emitting phosphate glass material based on divalent tin ions includes the following steps:

[0011] Calculate the weight of each component according to the molar percentage of the white light emitting phosphate glass material, and weigh the raw materials accordingly;

[0012] After grinding all the raw materials evenly to form a mixture, it is placed in a platinum crucible and preheated in a muffle furnace to reduce the generation of bubbles during the glass melting process.

[0013] The preheated platinum crucible was transferred to a silicon carbide rod electric furnace for melting. After homogenization and clarification, a uniform, bubble-free glass melt was obtained.

[0014] The molten glass is poured into a mold that has been preheated to 350°C, and then placed in a muffle furnace that has been heated to 300°C. After holding at this temperature for 2-3 hours, the muffle furnace is turned off and the glass is cooled to room temperature to obtain a glass block, which is a white light emitting phosphate glass material based on divalent tin ions.

[0015] Furthermore, the preheating temperature is 400°C and the time is 30 minutes.

[0016] Furthermore, the melting temperature is 1100℃ and the melting time is 60 minutes.

[0017] This invention provides a method for preparing Sn-based materials in air. 2+ A method for producing luminescent phosphate glass materials, through optimized glass composition design, can achieve luminescence of +2 valent Sn, with the precipitated crystalline phase being SnP2O7. This crystalline phase facilitates the luminescence of Sn in air. 2+ The white-light-emitting phosphate glass material prepared by this invention exhibits excellent comprehensive properties, a low glass transition temperature, good mechanical properties, and thermal stability. Furthermore, the addition of a suitable proportion of reducing agent further improves the efficiency of Sn emission without altering the glass structure and stability. 2+The luminous intensity of phosphate glass, after the addition of a reducing agent, is high when excited by a 290nm ultraviolet laser, with blue light emission intensity more than twice that of air. It is suitable for white LED lighting and display devices.

[0018] Compared with the prior art, the present invention has the following advantages and technical effects:

[0019] (1) The phosphate glass material of the present invention has high transparency, low melting point, uniform light emission, easy processing, high luminous efficiency, good thermal conductivity, good resistance to laser irradiation, and is suitable for white LEDs. It has high luminous efficiency, which is conducive to its promotion and application and has a broad market prospect.

[0020] (2) The present invention uses low-melting-point phosphate as the main glass raw material, which has a lower glass transition temperature, reduces the glass melting temperature, reduces the corrosive effect on phosphor during the melting process, and is conducive to improving the luminescence performance of fluorescent materials.

[0021] (3) The inventor discovered that when Sn 2+ When used as a luminescent center, if it is not intended that all Sn... 2+ It exists and can be produced in air; and the precipitated SnP2O7 crystal phase is conducive to the formation of Sn 2+ The luminescence of this material solves the problem that white light-emitting phosphate glass materials need to be prepared under a reducing atmosphere.

[0022] (4) In the preparation of phosphate glass, the present invention adds Si3N4 powder as a reducing agent, which further reduces the oxidation of divalent tin ions to tetravalent ions during the firing process, making it easy to produce on a large scale, which is conducive to improving production efficiency and reducing production costs. Attached Figure Description

[0023] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an undue limitation of this application. In the drawings:

[0024] Figure 1 The XRD patterns of the white light emitting phosphate glass materials based on divalent tin ions in Examples 1-5 of this invention are compared with the SnP2O7 PDF standard card.

[0025] Figure 2 The emission spectra of white light emitting phosphate glass materials based on divalent tin ions in Examples 1-5 of the present invention in the 300-600nm band under excitation by a 290nm laser pump source are shown.

[0026] Figure 3The XRD patterns of phosphate glass with a SnO concentration of 5% (molar percentage) and a reducing agent added in Examples 4 and 6-10 of this invention are compared with the SnP2O7 PDF standard card.

[0027] Figure 4 The excitation spectra of phosphate glass with a reducing agent and a SnO concentration of 5% (molar percentage) added in Examples 4 and 6-10 of the present invention in the 250-350 nm band under excitation by a 425 nm laser pump source, and the emission spectra in the 300-550 nm band under excitation by a 290 nm laser pump source. Detailed Implementation

[0028] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0029] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0030] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0031] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0032] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0033] Unless otherwise specified, the room temperature in the embodiments of the present invention is 25±2℃.

[0034] All raw materials used in the embodiments of the present invention were purchased commercially, and SnO, ZnO, ZnCl2 and P2O5 were purchased from Aladdin.

[0035] The technical solution of the present invention will be further illustrated by the following embodiments.

[0036] The glass compositions of Examples 1 to 5 are shown in Table 1.

[0037] Table 1 Glass composition of Examples 1 to 5

[0038]

[0039] Examples 1-5

[0040] (1) Calculate the weight of each component according to the molar percentage of glass composition in Table 1, and weigh each raw material component.

[0041] (2) After grinding the raw materials evenly to form a mixture, put it into a platinum crucible and preheat it in a muffle furnace at 400℃ for 30 minutes to reduce the generation of bubbles during the glass melting process;

[0042] (3) The crucible was then immediately transferred to a silicon carbide rod electric furnace at 1100°C and melted for 1 hour. After homogenization and clarification, a uniform glass melt without bubbles was obtained.

[0043] (4) Then quickly pour it into a mold that has been preheated to 350°C to form;

[0044] (5) Then put it into a muffle furnace that has been heated to 300°C, keep it at that temperature for 2-3 hours, then turn off the muffle furnace and cool it down to room temperature to obtain a glass block. After it has been completely cooled, take it out. This is the white light emitting phosphate glass material based on divalent tin ions.

[0045] The test results for this glass are as follows: Annealed glass blocks were cut and ground, and some were ground into powder for XRD testing (the same applies below). The results are as follows: Figure 1 As shown; some parts are processed into glass sheets and polished. The emission spectrum in the 300-600nm band under excitation by a 290nm laser pump source is shown below. Figure 2 As shown.

[0046] from Figure 1 It can be seen that as the SnO content increases, the crystallization peak shows a trend of first rising and then falling, with Example 4 reaching the highest point, where crystallization is most obvious. Combined with... Figure 2 The emission spectrum of the samples showed that the emission intensity was basically consistent with the crystallization peak, and also exhibited a trend of first increasing and then decreasing. The emission intensity of Examples 3 and 4 was much stronger than that of other examples, indicating that the precipitated SnP2O7 crystal phase is conducive to the precipitation of Sn. 2+ The light emitted.

[0047] Example 6

[0048] Same as Example 4, except that after step (1), 0.1 wt% Si3N4 powder reducing agent is added according to the total mass of white light emitting phosphate glass material raw materials SnO, ZnO, ZnCl2 and P2O5 before step (2).

[0049] Example 7

[0050] Same as Example 4, except that after step (1), 0.3wt% Si3N4 powder reducing agent is added according to the total mass of white light emitting phosphate glass material raw materials SnO, ZnO, ZnCl2 and P2O5 before step (2).

[0051] Example 8

[0052] Same as Example 4, except that after step (1), 0.5wt% Si3N4 powder reducing agent is added according to the total mass of white light emitting phosphate glass material raw materials SnO, ZnO, ZnCl2 and P2O5 before step (2).

[0053] Example 9

[0054] Same as Example 4, except that after step (1), 0.7wt% Si3N4 powder reducing agent is added according to the total mass of white light emitting phosphate glass material raw materials SnO, ZnO, ZnCl2 and P2O5 before step (2).

[0055] Example 10

[0056] Same as Example 4, except that after step (1), 1.0 wt% Si3N4 powder reducing agent is added according to the total mass of white light emitting phosphate glass material raw materials SnO, ZnO, ZnCl2 and P2O5 before step (2).

[0057] Figure 3 It can be seen that Example 4, without the reducing agent Si3N4 powder, exhibits a distinct tetravalent tin ion crystal phase; the crystallization peak of Example 6, after adding 0.1 wt% Si3N4 powder, is weakly present; and Examples 7-10 do not show any crystallization peak of tetravalent tin ions, indicating that tin ions mostly exist in the phosphate glass in a divalent state. Combined with... Figure 4 In Examples 4, 6-10, the excitation and emission light intensities all showed a trend of first increasing and then decreasing, which is related to the concentration of divalent tin ions.

[0058] The above are merely preferred embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A method for preparing a white light-emitting phosphate glass material based on divalent tin ions, characterized in that, Includes the following steps: Calculate the weight of each component according to the molar percentage of the white light emitting phosphate glass material, and weigh the raw materials accordingly; After grinding all raw materials evenly to form a mixture, the mixture is placed in a platinum crucible and preheated in a muffle furnace at a temperature of 400°C for 30 minutes. The preheated platinum crucible was transferred to a silicon carbide rod electric furnace for melting. After homogenization and clarification, a uniform, bubble-free glass melt was obtained. The melting temperature was 1100℃ and the time was 60 min. The molten glass is poured into a mold that has been preheated to 350 °C, and then placed in a muffle furnace that has been heated to 300 °C. After holding at this temperature for 2-3 hours, the muffle furnace is turned off and the temperature is lowered to room temperature to obtain a glass block, which is a white light emitting phosphate glass material based on divalent tin ions. The precipitated crystal phase is SnP2O7. The white light emitting phosphate glass material based on divalent tin ions comprises, by molar percentage, 2.5-25% SnO, 15-37.5% ZnO, 20% ZnCl2 and 40% P2O5; The raw materials of the white light emitting phosphate glass material based on divalent tin ions also include a reducing agent, which is Si3N4 powder. The amount of the reducing agent added is 0~1.0 wt% of the total mass of SnO, ZnO, ZnCl2 and P2O5 of the raw materials of the white light emitting phosphate glass material based on divalent tin ions, and is not 0.

2. The method for preparing white light-emitting phosphate glass material based on divalent tin ions according to claim 1, characterized in that, The raw material composition, in molar percentage, includes: 5% SnO, 35% ZnO, 20% ZnCl2 and 40% P2O5.

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